Polyalphaolefins and processes for forming polyalphaolefins

ABSTRACT

The invention is directed to polyalphaolefins (PAOs) and processes for forming PAOs. In one embodiment, the invention is to a process for forming a PAO comprising polymerizing C 8 -C 12  α-olefin monomers in the presence of hydrogen, a C 8 -C 12  saturated hydrocarbon, e.g., a C 8 -C 12  saturated straight-chain hydrocarbon, and a catalyst system in a reaction vessel, wherein the C 8 -C 12  saturated straight-chain hydrocarbon has about the same number of carbon atoms as the C 8 -C 12  α-olefin monomers. The C 8 -C 12  saturated straight-chain hydrocarbon optionally is derived from a crude PAO product formed by the process of the invention. The invention is also directed to reaction systems for performing the processes of the invention, to processes for controlling PAO viscosity based on residence time, and to the removal of spent catalyst using a solid adsorbent particles.

FIELD OF THE INVENTION

The present invention relates to polyalphaolefins. More particularly,the invention relates to polyalphaolefins and processes and reactionsystems for forming polyalphaolefins from an α-olefin, preferably aC₈-C₁₂ α-olefin such as 1-decene, by co-feeding to the polymerizationreaction mixture a C₈-C₁₂ saturated hydrocarbon, preferably having thesame number of carbon atoms as the α-olefin.

BACKGROUND OF THE INVENTION

Efforts to improve upon the performance of natural mineral oil basedlubricants by the synthesis of oligomeric hydrocarbon fluids have beenthe subject of important research and development in the petroleumindustry for several decades, leading to recent commercial production ofa number of polyalphaolefin synthetic lubricants. These materials areprimarily based on the polymerization of α-olefins, such as C₂-C₂₀α-olefins. Industrial research efforts on synthetic lubricants havegenerally focused on fluids exhibiting useful viscosities over a widerange of temperatures, i.e., having an improved viscosity index (VI),while also showing lubricity, thermal, and oxidative stability and pourpoint equal to or better than mineral oil. These newer syntheticlubricants provide lower friction and hence increased mechanicalefficiency across the full spectrum of mechanical loads and do so over awider range of operating conditions than mineral oil lubricants.

Well known structural and physical property relationships for polymersas contained in the various disciplines of polymer chemistry havepointed the way to α-olefins as a fruitful field of investigation forthe synthesis of oligomers with the structure thought to be needed toconfer improved lubricant properties thereon. Owing largely to studieson the polymerization of propene and vinyl monomers, the mechanism ofthe polymerization of α-olefins and the effect of that mechanism onpolymer structure is reasonably well understood, providing a strongresource for targeting on potentially useful oligomerization methods andoligomer structures.

Catalytic polymerization of olefins is a known technique formanufacturing basestocks useful as lubricants. There are various knownmethods for forming polyalphaolefins in the art, such as for example,U.S. Pat. Nos. 4,827,073; 4,892,851; 4,912,272; 5,012,020; 5,177,276;5,661,096; 5,731,254; 6,706,828; 6,858,767; and 7,129,197, the entiretyof which are incorporated herein by reference. Earlier catalyticpolymerization processes used chromium-based catalysts, as discussed inU.S. Pat. Nos. 4,827,073 and 5,012,020, Ziegler-type catalysts, such astitanium trichloride, as discussed in U.S. Pat. No. 5,177,276, andaluminum chloride, as discussed in U.S. Pat. No. 4,912,272. Theseearlier catalysts gave way to later developed processes using variousmetallocene catalysts and metallocene catalyst systems, as discussed,for example, in U.S. Pat. Nos. 4,892,851; 5,661,096; 5,731,254;6,706,828; 6,858,767; and 7,129,197. Such catalyst systems typicallycomprise the combination of: (a) a metallocene compound, typically ametallocene compound that is based on a Group IVb transition metal suchas zirconium, and (b) an aluminoxane. Unbridged substitutedbis-cyclopentadienyl transition metal metallocene compounds arediscussed in U.S. Published Application No. 2007/0043248.

The polyalphaolefins produced by such methods may, for example, be usedas lubricants or as lubricant additives, as discussed in U.S. Pub. App.Nos. 2006/0276355; 2007/0289897; and 2007/0298990, the entireties ofwhich are incorporated herein by reference.

U.S. Pat. No. 6,858,767 discloses that a liquid polyalphaolefin homo- orcopolymer, preferably 1-decene, which is substantially amorphous isobtained by a polymerization process employing hydrogen and a particulartype of metallocene catalyst. Additionally, liquid polyalphaolefin homo-or copolymer containing from 2 to about 12 carbon atoms possess a uniquecombination of properties, i.e., low molecular weight (M_(w)), lowpolydispersity index (M_(w)/M_(n)), controllable kinematic viscosity(Kv₁₀₀), low Iodine Number (I₂) and low glass transition temperature(T_(g)) and are substantially amorphous. The liquid polyalphaolefinhomo- or copolymers are useful for manufacturing a variety of productsincluding lubricating oils in which the polyalphaolefin functions as aviscosity modifier.

U.S. Pat. No. 7,129,197 discloses that one or more oligomers of anolefin are prepared in the presence of a single-site catalyst.Preferably, the olefin is an α-olefin, and the oligomer is apoly-alpha-olefin (PAO). The PAO so prepared is completely orsubstantially free of tertiary hydrogen resulting from isomerization.Consequently, the PAO possesses improved biodegradability, improvedoxidation resistance, and/or a relatively higher viscosity index. ThePAO has many useful applications, such as a component of a lubricant.

U.S. Pat. No. 5,177,276 discloses an alpha-olefin oligomer consistingessentially of repeating units having the structural formula:

wherein x represents an integer from 3 to 11, inclusive; and yrepresents the number of repeating units in the oligomer such that theweight average molecular weight is from about 5,000 to about 20,000;said oligomer having from about 70 to 100 percent head-to-tail alignmentof the repeating units of the oligomer. Preferably the weight averagemolecular weight of the oligomer is from 5,000 to about 10,000; and saidoligomer is further characterized as having a dispersity of less thanabout 5.5, and a Z average molecular weight of less than about 24,000.Additionally, U.S. Pat. No. 5,177,276 discloses recycling unconvertedfeed, which usually contains saturated alpha-olefin, to theoligomerization process to serve as the reaction solvent.

U.S. Pat. No. 5,731,254 discloses a syndiotactic polyolefin is obtainedin a high yield by polymerization or copolymerization of an olefin ofthe formula R^(a)—CH═CH—R^(b) in the presence of a catalyst consistingof a metallocene of the formula I

in which M₁ is titanium, zirconium, vanadium, niobium or tantalum, andan aluminoxane. This polyolefin has a very high molecular weight, a verynarrow molecular weight distribution and a very high syndiotactic index.Shaped articles produced from the polymer are distinguished by a hightransparency, flexibility, tear resistance and an excellent surfacegloss.

U.S. Pat. No. 4,892,851 discloses a metallocene catalyst for use inpreparing syndiotactic polyolefins. The catalyst comprises a bridgedmetallocene in which one of the cyclopentadienyl rings is substituted ina substantially different manner from the other ring. It was discoveredthat this type of catalyst is highly syndiospecific, and it alsoproduces a polymer with a novel microstructure. The invention furtherincludes the use of one or more of the catalysts in a polymerizationprocess. The catalyst is generally described by the formula

R−(CpR_(n))(CpR′_(m))MeQ_(k)

wherein each Cp is a cyclopentadienyl or substituted cyclopentadienylring; each R_(n) and R′_(m) is the same or different and is ahydrocarbyl radical having 1-20 carbon atoms; R″ is a structural bridgebetween the two Cp rings imparting stereorigidity to the catalyst; Me isa group 4b, 5b, or 6b metal from the Periodic Table of Elements; each Qis a hydrocarbyl radical having 1-20 carbon atoms or is a halogen;0≦k≦3; 0≦n≦4; 1≦m≦4; and wherein R′_(m) is selected such that (CpR′_(m))is a sterically different ring than (CpR_(n)).

U.S. Pat. No. 4,827,073 discloses a process for oligomerizing alphaolefin to produce lubricant range hydrocarbon stock including the stepof contacting said alpha olefin with a supported solid reduced Group VIB(e.g., chromium) catalyst under oligomerization conditions at atemperature of about 90° to 250° C. to produce liquid lubricanthydrocarbon. The product comprises the polymeric residue of linearC₆-C₂₀ 1-alkenes, said composition having a branch ratio of less than0.19. The weight average molecular weight is between 420 and 45,000,number average molecular weight between 420 and 18,000, molecular weightdistribution between 1 and 5 and pour point below −15° C. Thehydrogenated lubricant range hydrocarbon product has viscosity index ofabout 130 to 280 and viscosity up to about 750 cS. The process isparticularly useful where the starting alpha olefin consists essentiallyof olefinic hydrocarbon having 8 to 14 carbon atoms or mixtures thereof;wherein the process conditions include reaction temperature of about100° to 180°; and wherein the support catalyst includes porous inertsilica.

U.S. Pat. No. 5,661,096 discloses Ziegler catalysts based on ametallocene as the transition metal component and an aluminoxane as theactivator, preactivation of the metallocene with the aluminoxane resultsin a considerable increase in the activity of the catalyst system.Furthermore, 1-olefin polymers of a high degree of isotacticity andhaving compact, spherical particles, a very narrow particle sizedistribution and a high bulk density are obtained by means of a catalystsystem of this type.

U.S. Pat. No. 5,012,020 discloses a novel composition is disclosed thatis particularly useful as a lubricant viscosity index improver. Thecomposition comprises branched branched C₃₀-C₁₀₀₀₀ hydrocarbons thathave a branch ratio of less than 0.19 and viscosity at 100° C. between725 CS and 15,000 cS. The novel compositions comprise the product of theoligomerization of C₆ to C₂₀ alpha-olefin feedstock, or mixturesthereof, under oligomerization conditions at a temperature between −20°C. and +90° C. in contact with a reduced valence state Group VIB metalcatalyst on porous support. The compositions have viscosities at 100° C.between 725 cS and 15,000 cS. Using the foregoing compositions inadmixture with mineral oil and synthetic lubricants provides novellubricant blends that show an elevated viscosity index. The mixturesalso show an increased stability to shear stress at high temperaturewith all blends notable by exhibiting Newtonian flow.

U.S. Pat. No. 4,912,272 discloses a lubricant mixtures havingunexpectedly high viscosity indices. The mixtures are blends of highviscosity index polyalphaolefins (HVIXPAO) prepared with activatedchromium on silica catalyst and polyalphaolefins prepared with BF3,aluminum chloride, or Ziegler-type catalyst. Superior blends are alsoprepared from HVIXPAO with mineral oil and/or other synthetic liquidlubricants.

U.S. Pat. No. 6,706,828 discloses a process for the preparation of apoly(α-olefin) polymer wherein the process comprises polymerizing atleast one α-olefin in the presence of hydrogen and a catalyticallyeffective amount of catalyst comprising the product obtained bycombining a metallocene catalyst with a cocatalyst, the metallocenecatalyst being at least one meso compound of general formula:

wherein: A¹ and A² are independently selected from the group consistingof mononuclear and polynuclear hydrocarbons;

M¹ is a metal from group IVb, Vb, or VIb of the Periodic Table;

R¹ and R² are independently selected from the group consisting ofhydrogen, C₁-C₁₀ alkyl, C₁-C₁₀-alkoxy, C₆-C₁₀ aryl, C₆-C₁₀ aryloxy,C₂-C₁₀ alkenyl, C₇-C₄₀ arylalkyl, C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyland halogen;

R⁷ is selected from the group consisting of:

═BR¹¹, ═AlR¹¹, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO₂, ═NR¹¹, ═CO, ═PR¹¹ and═P(O)R¹¹, where

R¹¹, R¹², and R¹³ are independently selected from the group consistingof hydrogen, halogen, C₁-C₁₀ alkyl, C₁-C₁₀ fluoroalkyl, C₆-C₁₀ aryl,C₆-C₁₀ fluoroaryl, C₁-C₁₀ alkoxy, C₂-C₁₀ alkenyl, C₇-C₄₀ arylalkyl,C₈-C₄₀ arylalkenyl, and C₇-C₄₀ alkylaryl, or R¹¹ and R¹² or R¹¹ and R¹³,in each case with the atoms connecting them, form a ring; and M² isselected from the group consisting of silicon, germanium, and tin;

R⁸ and R⁹ are independently selected from the group consisting ofhydrogen, halogen, C₁-C₁₀ alkyl, C₁-C₁₀ fluoroalkyl, C₆-C₁₀ aryl, C₆-C₁₀fluoroaryl, C₁-C₁₀ alkoxy, C₂-C₁₀ alkenyl, C₇-C₄₀ arylalkyl, C₈-C₄₀arylalkenyl, and C₇-C₄₀ alkylaryl; m and n are identical or differentand are zero, 1, or 2, with m plus n being zero, 1 or 2.

Regardless of the catalyst system and process parameters employed, ithas been difficult to directly produce lower viscosity rangepolyalphaolefins, e.g., polyalphaolefins having a viscosity ofapproximately 100 cSt or below, without incurring lower selectivity andyields due to the simultaneous production of higher viscosity byproductsand higher molecular weight oligomers and polymers. Thus, a significantproblem in the manufacture of synthetic lubricants is the production oflubricants in a preferred viscosity range at high selectivity, andyield, as well as conversion. Thus, the need exists for processes andreaction systems for forming polyalphaolefins of desired lubricantviscosity at high conversion, selectivity and yield.

SUMMARY OF THE INVENTION

The present invention is directed to high selectivity processes forforming polyalphaolefins (PAOs) from an α-olefin monomer. It hassurprisingly and unexpectedly been discovered that the addition of asaturated hydrocarbon, preferably a saturated hydrocarbon having aboutthe same number of carbon atoms as the α-olefin monomer, to a PAOreaction vessel with the α-olefin monomer in the presence of hydrogenand a suitable catalyst system increases selectivity while maintainingdesirable physical characteristics for the resulting PAO such asviscosity, viscosity index, Iodine Number, molecular weight (M_(w) andM_(n)) and tacticity, relative to similar systems in which suchhydrocarbons are not or are minimally co-fed to the reaction system.

In a first embodiment, the process comprises the steps of adding aC₈-C₁₂ α-olefin, a C₈-C₁₂ saturated hydrocarbon, hydrogen, and acatalytically effective amount of a catalyst system to a reactionvessel, wherein the C₈-C₁₂ saturated hydrocarbon is fed to the reactionvessel in an amount ranging from 5 to 70 weight percent, e.g., from 10to 50 weight percent or from 15 to 30 weight percent, based on thecombined weight of the C₈-C₁₂ α-olefin and the C₈-C₁₂ saturatedhydrocarbon fed to the reaction vessel; and polymerizing the C₈-C₁₂α-olefin in the reaction vessel in the presence of the C₈-C₁₂ saturatedhydrocarbon, the hydrogen, and the catalyst system under conditionseffective to form the PAO. The process preferably is a continuousprocess.

In a second embodiment, the invention is to a process, preferably acontinuous process, for forming a PAO, comprising the steps of adding anα-olefin, a hydrocarbon having a 50° C. vapor pressure within 20%, e.g.,within 10% or within 5%, of the vapor pressure of the α-olefin,hydrogen, and a catalytically effective amount of a catalyst system to areaction vessel; and polymerizing the α-olefin in the reaction vessel inthe presence of the hydrocarbon, the hydrogen, and the catalyst systemunder conditions effective to form the PAO.

In the above embodiments, the olefin, e.g., the C₈-C₁₂ α-olefin and thehydrocarbon, e.g., C₈-C₁₂ saturated hydrocarbon, optionally have thesame number of carbon atoms, optionally within 1 carbon atom. Forexample, if the C₈-C₁₂ α-olefin comprises 1-decene, then the C₈-C₁₂saturated hydrocarbon preferably comprises a decane such as n-decane.The hydrocarbons, e.g., C₈-C₁₂ saturated hydrocarbons, optionally aremaintained in the reaction vessel at a level of from 8 to 40 weightpercent, based on the combined weight of the C₈-C₁₂ α-olefin, the C₈-C₁₂saturated hydrocarbon, and the PAO in the reaction vessel. The catalystsystem preferably comprises a metallocene catalyst, e.g., a bridgedmetallocene catalyst such as diphenylmethylene(cyclopentadienyl-9-fluorenyl)zirconium dichloride, and optionallyfurther comprises an aluminoxane cocatalyst, e.g., methylaluminoxane(MAO). As indicated above, in either embodiment, the process typicallyis highly selective, e.g., providing a PAO selectivity greater than 80wt. %, greater than 85 wt. %, greater than 90 wt. % or greater than 95wt. %. Additionally, the process typically has high overall conversion,e.g., greater than 95 percent, and a high yield, e.g., greater than 85percent, greater than 90 percent, or greater than 95 percent. Thepolymerization processes optionally are conducted at a temperatureranging from 105° C. to 170° C., and preferably at a pressure from 520to 720 kPag. The process preferably has a PAO residence time of from 10to 60 minutes, e.g., from 15 to 45 minutes.

In a preferred aspect, the process initially forms a crude PAO productcomprising the PAO, unreacted monomer, and C₈-C₁₂ saturated hydrocarbon,and the process further comprises the steps of separating the C₈-C₁₂saturated hydrocarbons from the crude PAO product, and adding at least aportion of the separated C₈-C₁₂ saturated hydrocarbons to the reactionvessel. Optionally, a first portion of the separated C₈-C₁₂ saturatedhydrocarbons is purged, and a second portion of the separated C₈-C₁₂saturated hydrocarbons is added to the reaction vessel. The unreactedmonomer may be separated from the crude PAO product with the separatedC₈-C₁₂ saturated hydrocarbons and added to the reaction vessel with theseparated C₈-C₁₂ saturated hydrocarbons. Optionally, the process furthercomprises the step of contacting a crude PAO product from the reactionvessel with solid adsorbent particles packed in a catalyst removalcolumn under conditions effective to selectively adsorb spent catalystfrom the PAO reaction system.

In another embodiment, the invention is to a novel PAO composition,which, in one embodiment, may be formed by the above processes of thepresent invention. The PAO comprises from 0.5 to 5 mole % of mm triadsand from 40 to 58 mole % of rr triads, as determined by ¹³C NMR. The PAOalso preferably comprises from 37 to 59.5 mole % of mr triads. The PAOideally is substantially free of peaks in a region of from 27.0 to 29.0ppm, and/or in a region of about 20.0 ppm and/or in a region of about42.5 ppm in a ¹³C NMR spectrum. The PAO preferably has a high degree ofsaturation, and ideally has an Iodine Number of from 0.2 to 5. The PAOpreferably is formed by polymerizing an olefin monomer, e.g., a C₈-C₁₂olefin, preferably 1-decene, in the presence of a metallocene catalyst,preferably a bridged metallocene, and hydrogen, as described above. Theviscosity of the PAO may vary, but preferably the PAO has a kinematicviscosity at 100° C. from 50 to 500 centistokes, e.g., from 50 to 150centistokes.

In another embodiment, the invention is directed to a catalyst removalcolumn in fluid communication with a PAO reaction vessel. The catalystremoval column is packed with solid adsorbent particles configured toselectively adsorb spent catalyst from the PAO reaction system. Thesolid adsorbent particles may, for example, be selected from the groupconsisting of acidic clay, zeolites, calcium oxide, magnesium oxide,silicates and mixtures thereof. Optionally, the solid adsorbent isdried, using methods known in the art, to remove any moisture. In apreferred aspect, the solid adsorbent particles comprise a metal oxide.The solid adsorbent particles may have an average particle size of from100 μm to 1 cm. Since the catalyst removal column does not employ waterto deactivate the catalyst, the catalyst removal column is particularlywell suited for being employed in the PAO synthesis processes in whichat least a portion of a crude PAO product is to be recycled to thereaction vessel.

In another embodiment, the invention is to a process for controlling PAOviscosity based on PAO residence time. Specifically, it has surprisinglyand unexpectedly been discovered that residence time has an inverserelationship on PAO viscosity. In this aspect, the invention is to aprocess for forming a PAO, comprising the step of polymerizing in areaction vessel a C₈-C₁₂ α-olefin in the presence of hydrogen, and acatalytically effective amount of a catalyst system under conditionseffective to form the PAO. The PAO has an average residence time in thereaction vessel of greater than 1 minute, and the PAO has a kinematicviscosity of less than 1000 cSt, e.g., less than 500 cSt, less than 250cSt, less than 150 cSt, or less than 100 cSt. Preferably, the PAO has anaverage residence time in the reaction vessel of greater than 5 minutes,and the PAO has a kinematic viscosity of less than 200 cSt, e.g., lessthan 150 cSt, or less than 100 cSt. More preferably, the PAO has anaverage residence time in the reaction vessel of greater than 10minutes, and the PAO has a kinematic viscosity of less than 150 cSt,e.g., less than 125 cSt, or less than 100 cSt. As with the aboveprocesses, one or more C₈-C₁₂ saturated hydrocarbon, preferably have thesame number of carbon atoms as the α-olefin, may be co-fed to thereaction vessel. Preferably, the C₈-C₁₂ α-olefin comprises 1-decene and,if present, the C₈-C₁₂ saturated hydrocarbon comprises n-decane. Thecatalyst system preferably comprises a metallocene catalyst, e.g., abridged metallocene catalyst such as diphenylmethylene(cyclopentadienyl-9-fluorenyl)zirconium dichloride, and optionallyfurther comprises an aluminoxane cocatalyst, e.g., methylaluminoxane(MAO).

In another embodiment, the invention is to a reaction system for formingPAO, preferably a continuous reaction system for forming PAO. Thereaction system comprises a reaction vessel in which a C₈-C₁₂ α-olefincontacts a C₈-C₁₂ saturated hydrocarbon, hydrogen, and a catalyticallyeffective amount of catalyst system under conditions effective to form acrude PAO stream. The system also includes a catalyst separation unit influid communication with the reaction vessel for separating spentcatalyst from the crude PAO stream and forming a reduced catalyst PAOstream. The reaction system further comprises a separation zone in fluidcommunication with the catalyst separation unit for separating thereduced catalyst PAO stream into a purified PAO stream and a recyclestream comprising the C₈-C₁₂ saturated straight-chain hydrocarbon andunreacted C₈-C₁₂ α-olefin. According to this embodiment, the recyclestream is in fluid communication between the separation zone and thereaction vessel. The C₈-C₁₂ α-olefin and the C₈-C₁₂ saturatedhydrocarbon preferably have the same number of carbon atoms. Preferably,the C₈-C₁₂ α-olefin comprises 1-decene and the C₈-C₁₂ saturatedhydrocarbon comprises n-decane. The catalyst system preferably comprisesa metallocene catalyst, e.g., a bridged metallocene catalyst such asdiphenylmethylene (cyclopentadienyl-9-fluorenyl)zirconium dichloride,and optionally further comprises an aluminoxane cocatalyst, e.g., MAO.

In another embodiment, the invention is to a reaction system, preferablya continuous reaction system, for forming PAO, comprising a reactionvessel in which an α-olefin contacts a hydrocarbon having a 50° C. vaporpressure within 20%, e.g., within 10% or within 5%, of the α-olefin,hydrogen, and a catalytically effective amount of catalyst system underconditions effective to form a crude PAO stream. The system alsoincludes a catalyst separation unit in fluid communication with thereaction vessel for separating spent catalyst from the crude PAO streamand forming a reduced catalyst PAO stream. A separation zone is in fluidcommunication with the catalyst separation unit for separating thereduced catalyst PAO stream into a purified PAO stream and a recyclestream comprising the hydrocarbon and unreacted α-olefin. The recyclestream is in fluid communication between the separation zone and thereaction vessel. The hydrocarbon preferably comprises a saturatedhydrocarbon having an equal number of carbon atoms, within 1 carbonatom, as the α-olefin. Preferably, the α-olefin comprises 1-decene andthe hydrocarbon comprises n-decane. The catalyst system preferablycomprises a metallocene catalyst, e.g., a bridged metallocene catalystsuch as diphenylmethylene (cyclopentadienyl-9-fluorenyl)zirconiumdichloride, and optionally further comprises an aluminoxane cocatalyst,e.g., MAO.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will be better understood in view of the appendednon-limiting figures, in which:

FIG. 1 is an exemplary flow diagram of a reaction system for formingpolyalphaolefin (“PAO”) according to one embodiment of the invention;

FIG. 2 is an exemplary flow diagram of a reaction system for forming PAOaccording to another embodiment of the invention;

FIG. 3 is an exemplary flow diagram of a reaction system for forming PAOaccording to another embodiment of the invention;

FIG. 4 is a table providing exemplary relative flow rates of variouscomponents contained in the effluent streams of the reaction system ofFIG. 2;

FIG. 5A is a ¹³C NMR spectra in accordance to one embodiment of thepresent invention compared with a first comparative example;

FIG. 5B is a detail portion of the ¹³C NMR spectrum of FIG. 5A;

FIG. 6 is a ¹³C NMR spectrum of the PAO formed in Example 8;

FIG. 7 is a ¹³C NMR spectrum of a second comparative example; and

FIG. 8 is a chart plotting viscosity as a function of residence timeaccording to Examples 4-6.

DETAILED DESCRIPTION OF THE INVENTION Introduction

In a first embodiment, the present invention relates to processes forforming polyalphaolefins (“PAOs”) from an α-olefin monomer, preferably aC₈-C₁₂ α-olefin monomer, more preferably 1-decene monomer. In thisembodiment, the invention is to a process for polymerizing C₈-C₁₂α-olefins, such as 1-decene, in the presence of hydrogen and acatalytically effective amount of a catalyst (or catalyst system) toform oligomers and/or polymers having viscosities and other physicalproperties suitable for synthetic lubricant applications. In thisembodiment, a C₈-C₁₂ saturated hydrocarbon, preferably saturatedstraight-chain hydrocarbon, preferably having the same number of carbonatoms as the C₈-C₁₂ α-olefin monomer, is co-fed to the reaction mixturewith the monomer. For example, if the monomer comprises 1-decene, thenthe saturated straight or branched chain hydrocarbon preferablycomprises one or more decanes (in particular n-decane). In thisembodiment, the C₈-C₁₂ saturated hydrocarbon, preferably saturatedstraight-chain hydrocarbon, is ideally present in the feed in an amountranging from 5 to 50 weight percent, preferably in an amount rangingfrom 10 to 50 weight percent, and most preferably in an amount rangingfrom 15 to 30 weight percent, based on the weight of the α-olefinmonomer (e.g., the C₈-C₁₂ α-olefin monomer) and the C₈-C₁₂ saturatedhydrocarbon in the feed.

It has surprisingly and unexpectedly been discovered that by maintaininga heightened concentration of saturated hydrocarbons in the reactionmixture, the overall selectivity and yield of the resulting process maybe advantageously increased. This increase in selectivity and yielddesirably and surprisingly is not generally accompanied by a significantchange in PAO viscosity. In addition, the process of this embodiment ofthe present invention may provide improved conversion. Optionally, theC₈-C₁₂ saturated hydrocarbon is derived from a crude PAO byproductformed in the polymerization process.

In a second embodiment, the invention relates to a process for forming aPAO, comprising the steps of: (a) polymerizing an α-olefin monomer,preferably a C₈-C₁₂ α-olefin monomer, more preferably a 1-decenemonomer, in the presence of hydrogen, and a catalyst system in areaction vessel, and (b) adding a hydrocarbon to the reaction vessel. Inthis embodiment, the hydrocarbon has a vapor pressure within 20%, e.g.,within 10% or within 5%, of the vapor pressure of the pure α-olefinmonomer (as measured at 50° C.). Preferably, the hydrocarbon comprises asaturated hydrocarbon, e.g., a saturated hydrocarbon having asubstantially equal number of carbon atoms, within 1 carbon atom, as themajor α-olefin monomer. More preferably, the hydrocarbon comprises aC₈-C₁₂ saturated hydrocarbon, preferably having the same number ofcarbon atoms as the major α-olefin monomer. As with the firstembodiment, the hydrocarbon optionally is derived from a crude PAOproduct formed in the polymerization process. Similarly, the hydrocarbonoptionally is present in the feed in an amount ranging from 5 to 50weight percent, preferably in an amount ranging from 10 to 50 weightpercent, and most preferably in an amount ranging from 15 to 30 weightpercent, based on the combined weight of the α-olefin monomer(preferably the C₈-C₁₂ α-olefin monomer) and the hydrocarbon fed to thereaction vessel.

In a third embodiment, the present invention is directed to reactionsystems suitable for performing the inventive processes of theinvention.

In a fourth embodiment, the invention is to a catalyst removal columnthat is particularly well-suited for use in a continuous PAO reactionsystem. The catalyst removal column is in fluid communication with a PAOreaction vessel, and is packed with solid adsorbent particles configuredto selectively adsorb spent catalyst from the PAO reaction system. Thisembodiment may be desired for those aspects in which a portion of theproduct is recycled back to the reaction vessel, as described above,because the column allows for the efficient separation of spent catalystfrom the crude effluent stream without the use of water, which, ifrecycled to the reaction vessel, would deactivate the metallocenecatalyst system.

In a fifth embodiment, the invention is to a process for forming a PAOin which the kinematic viscosity of the PAO is controlled based on theresidence time of the PAO in the reaction vessel. The process comprisesthe step of polymerizing in a reaction vessel a C₈-C₁₂ α-olefin in thepresence of hydrogen and a catalytically effective amount of a catalyst(or catalyst system) under conditions effective to form the PAO, whereinthe PAO has an average residence time in the reaction vessel of greaterthan 1 minute, and wherein the PAO has a kinematic viscosity of nogreater than 500 cSt.

Monomers

As indicated above, in the processes of the invention an α-olefinmonomer, preferably a C₈-C₁₂ α-olefin monomer, is polymerized in thepresence of hydrogen and a catalytically effective amount of catalyst(or a catalyst system) to form PAO. The α-olefin preferably is selectedfrom the group consisting of 1-octene, 1-nonene, 1-decene, 1-undecene,and 1-dodecene, more preferably is selected from the group consisting of1-octene, 1-decene, and 1-dodecene, and most preferably is 1-decene. Thepurity level of the α-olefin employed, preferably 1-decene, ideally, butnot necessarily, is greater than 90 wt. %, e.g., greater than 94 wt. %or greater than 98 wt. %.

The amount of α-olefin that is added to the reaction vessel may varydepending, for example, on the activity of the catalyst employed. Insome exemplary embodiments, the α-olefin monomer, e.g., C₈-C₁₂ α-olefin,is added to the reaction vessel in an amount ranging from 10 to 95weight percent, e.g., from 50 to 95 weight percent or from 70 to 93weight percent, based on the total weight of all material fed to thereaction vessel. Ideally, the C₈-C₁₂ α-olefin monomer comprises 1-decenein an amount greater than 75 weight percent, e.g., greater than 90weight percent or greater than 99 weight percent, based on the totalweight of C₈-C₁₂ α-olefin monomer added to the reaction vessel.

Optionally, the C₈-C₁₂ α-olefin monomer comprises a major C₈-C₁₂α-olefin monomer, e.g., 1-decene, in combination with one or more minormonomers. As used herein, a “major” C₈-C₁₂ α-olefin monomer is a C₈-C₁₂α-olefin monomer that is present in a polymerization feedstock in anamount greater than or equal to 50 weight percent, based on totalmonomer contained in the feedstock. Conversely, for purposes of thepresent specification, a “minor” monomer is a monomer that is present ina polymerization feedstock in an amount less than 50 weight percent,based on total monomer contained in the feedstock. Thus, the PAO that isformed in the processes of the invention may be a homopolymer of anα-olefin monomer, e.g., a C₈-C₁₂ α-olefin monomer such as 1-decene, or acopolymer of a major C₈-C₁₂ α-olefin monomer and one or more minormonomers. The minor monomers(s) may comprise, for example, one or moreC₂-C₂₅ monomers, preferably one or more C₂-C₂₅ α-olefins. Thecombination of two or more monomers in the polymerization reactionmixture may be desirable, for example, to control the branchingcharacteristics and viscosity of the resulting PAO product that isformed, as described, for example, in U.S. patent application Ser. No.12/026,981, filed Feb. 6, 2008, entitled “Controlling Branch Level andViscosity of Polyalphaolefins with Propene Addition,” the entirety ofwhich is incorporated herein by reference. For example, in someexemplary embodiments, the monomer feedstock may comprise: (1) fromabout 75 weight percent to about 99 weight percent major C₈-C₁₂ α-olefinmonomer (such as 1-decene), e.g., from about 80 weight percent to about90 weight percent major C₈-C₁₂ α-olefin monomer, from about 85 weightpercent to about 95 weight percent major C₈-C₁₂ α-olefin monomer, orfrom about 90 weight percent to about 99 weight percent major C₈-C₁₂α-olefin monomer; and (2) from about 1 weight percent to about 25 weightpercent minor monomer(s) (such as propene), e.g., from about 10 weightpercent to about 20 weight percent minor monomers, from about 5 weightpercent to about 15 weight percent minor monomers, or from about 1weight percent to about 10 weight percent minor monomers. The minormonomers may include, for example, one or more of the following:ethylene, propylene, 2-methylpropene, 1-butene, 3-methyl-1-butene,1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene,1-eicosene, and the like. If the monomers employed include decene andone or more minor monomers, then the weight ratio of the decene to theone or more minor monomers in the polymerization reaction mixturepreferably is greater than 3:1, e.g., greater than 4:1, greater than5:1, greater than 10:1, greater than 20:1 or greater than 50:1.

Hydrogen

The monomers employed in the processes of the invention preferably areconverted to PAOs in the presence of hydrogen. A key role of hydrogen inthe reaction is to hydrogenate residual unsaturation left in the PAOmolecules. Thus, the presence of hydrogen in the reaction vessel mayadvantageously result in the elimination of the need for an additionalhydrogenation step after formation of the PAO. Unfortunately, hydrogenmay add to the unsaturation in the monomer α-olefin to form a saturatedbyproduct which is generally unreactive. It is therefore desirable topromote the hydrogenation of PAO over the hydrogenation of the α-olefin.Desirably, however, the formation (and/or addition) of saturated monomerreduces the overall viscosity of the reaction mixture and may enhancehydrogen solubility. Without being bound by theory, enhancing hydrogensolubility may enable better diffusion of hydrogen through the reactionmixture to the unsaturation sites of the PAO. The net result of theimproved mass transfer of hydrogen to the PAO is a favorable shift inthe relative reaction rates of PAO hydrogenation over α-olefinhydrogenation, and thus a reduction in the amount of monomer that ishydrogenated resulting in improved selectivity and yield. See, forexample, Published U.S. Patent Appl. No. 2007/0043248, filed Jul. 19,2006, the entirety of which is incorporated herein by reference.

By carrying out the polymerization reaction in the presence of hydrogenand employing the catalysts described herein, the liquid PAOs formed bythe processes of the invention are substantially saturated and,therefore, will possess a low Iodine Number, e.g., an Iodine Number offrom about 0.0 to about 10, preferably from about 0.1 to about 5, morepreferably from about 0.2 to about 5, and most preferably from about 0.2to about 3. As used herein, Iodine Number refers to the mass of iodinein grams that is consumed by 100 grams of polymer. In a preferredembodiment, and for purposes of the present specification, Iodine Numberis determined as described in Gallo et al., “Unsaturation inIsoprene-Isobutylene Copolymers”, Industrial and Engineering Chemistry,Vol. 40, (1948) pp. 1277-1280, the entirety of which is incorporatedherein by reference, but using o-dichlorobenzene as solvent, a 0.8 gsample size, 50% of the associated reagent volumes, and without reflux.

Preferably, the monomer and the hydrogen are co-fed into thepolymerization reaction vessel. By “co-fed” it is meant that the monomerand hydrogen are fed to the reaction vessel simultaneously, at least inpart (whether in a single combined stream or separate streams). In oneaspect, hydrogen is added to the reaction vessel separately from themonomer feedstock. For example, the hydrogen may be added directly tothe reaction mixture through a sparging system. Additionally oralternatively, the hydrogen may be added to the monomer feedstock,optionally under pressure, prior to addition to the reaction vessel.

The amount of hydrogen fed to the reaction vessel may vary widelydepending, for example, on the desired degree of hydrogenation, and theactivity of the catalyst system that is employed. Optionally, hydrogenis added to the reaction vessel in an amount greater than 0.01 moleshydrogen per mole of monomer, e.g., greater than 0.04 moles hydrogen permole of monomer or greater than 0.08 moles hydrogen per mole of monomer.In terms of ranges, optionally from 0.01 to 1.2 moles of hydrogen arefed to the reaction vessel per mole of monomer, e.g., from 0.04 to 0.76moles hydrogen per mole of monomer or from 0.08 to 0.12 moles hydrogenper mole of monomer.

In some exemplary embodiments, the flow rate of hydrogen to the reactionvessel is from 10 to 10,000 standard cubic centimeters per minute (sccm)per liter of reactor, e.g., from 10 to 5,000 sccm per liter of reactor,or from 500 to 1000 sccm/min per liter of reactor.

Hydrocarbon

As indicated above, in some aspects of the invention, a saturatedhydrocarbon, e.g., a C₈-C₁₂ saturated hydrocarbon, preferably a C₈-C₁₂saturated straight chain hydrocarbon, is co-fed to the reaction mixturewith the α-olefin monomer, e.g., the C₈-C₁₂ α-olefin monomer. In apreferred embodiment, the hydrocarbon has the same number of carbonatoms as the major C₈-C₁₂ α-olefin monomer. Similarly, in someembodiments, a hydrocarbon (preferably a saturated hydrocarbon having asubstantially equal number of carbon atoms, within 1 carbon atom, as themajor α-olefin monomer) having a 50° C. vapor pressure within 20%, e.g.,within 10% or within 5%, of the vapor pressure of the major α-olefinmonomer that is added to the polymerization reaction vessel is co-fed tothe reaction mixture with the major α-olefin monomer.

It has surprisingly and unexpectedly been discovered that by co-feedinga saturated hydrocarbon, e.g., a C₈-C₁₂ saturated hydrocarbon,preferably a C₈-C₁₂ saturated straight chain hydrocarbon, with monomerto the reaction vessel, selectivity and yield may be advantageouslyincreased. The level of saturated hydrocarbons that is co-fed to thereaction system may vary depending on conditions such as the activity ofthe catalyst system and process conditions employed, but preferably isless than 40 weight percent, e.g., less than 30 weight percent or lessthan 20 weight percent (but preferably is greater than 5 weight percent,e.g., greater than 10 weight percent or greater than 15 weight percent),based on the combined weight of the α-olefin monomer (e.g., the C₈-C₁₂α-olefin monomer) and C₈-C₁₂ saturated hydrocarbon fed to the reactionvessel. In a preferred aspect, the saturated hydrocarbon level in thereaction vessel is maintained substantially constant. In particularlypreferred embodiments, the saturated hydrocarbons are fed to (ormaintained in) the reaction vessel at a level ranging from 5 to 50weight percent, e.g., from 8 to 30 weight percent, from 10 to 50 weightpercent, from about 10 to about 25 weight percent, or from 15 to 30weight percent, based on the combined weight of the α-olefin monomer(e.g., the C₈-C₁₂ α-olefin monomer) and the C₈-C₁₂ saturated hydrocarbonfed to the reaction vessel. The weight ratio of the monomer tohydrocarbon in the feed (whether separate or combined) optionally isless than 19:1, e.g., less than 9:1, less than 5.7:1 or less than 2.3:1,and, in terms of ranges, may range from 1:1 to 19:1, e.g., from 9:1 to19:1, or from 2.3:1 to 5.7:1. These saturated hydrocarbon levels havesurprisingly and unexpectedly shown to effectively maximize selectivityand yield, while maintaining commercially acceptable levels of overallPAO production.

Without being bound by theory, the selectivity and yield are believed tobe improved by improving access of the hydrogen in the reaction systemto unsaturated PAO relative to the monomer. For example, when 1-deceneis used as the monomer and a decane, e.g., n-decane, is employed as thesaturated hydrocarbon, any unsaturated polydecene formed from the1-decene monomer may be hydrogenated to a greater extent than theunsaturated polydecene that would be present in a reaction system underthe same conditions but in the absence of the saturated hydrocarbon.Conversely, the monomer in the reaction system containing the saturatedhydrocarbon, particularly in the amounts claimed, will be less likely tobe hydrogenated to form additional saturated hydrocarbons (e.g., formingn-decane from 1-decene) relative to monomer that would be present in areaction system under the same conditions but in the absence of thesaturated hydrocarbon. Thus, the presence of the saturated hydrocarbon,e.g., decane, should suppress formation of additional n-decane, therebyimproving overall selectivity and yield.

Saturated hydrocarbons, e.g., C₈-C₁₂ saturated hydrocarbons, preferablyC₈-C₁₂ saturated straight-chain hydrocarbons, may be formed as abyproduct of the PAO polymerization processes of the present invention.Accordingly, a crude PAO product that is yielded from the reactionvessel optionally may be separated in one or more separation units intoan enriched saturated hydrocarbon stream and a purified PAO productstream comprising purified PAO. If more than one separation unit (e.g.,distillation column, evaporator (preferably a wiped film evaporator),flash vessel, etc.) is employed in the separation step, then theenriched saturated hydrocarbon stream may comprise, for example, one ormore overhead streams from the multiple separation units. Similarly, ifmore than one separation unit is employed in the separation step, thenthe purified PAO product stream may comprise, for example, one or morebottoms streams from the multiple separation units.

The concentration of the hydrocarbon (e.g., the C₈-C₁₂ saturatedstraight-chain hydrocarbon such as one or more decanes or thehydrocarbon having a 50° C. vapor pressure within 20%, e.g., within 10%or within 5%, of the α-olefin) contained in the enriched saturatedhydrocarbon stream will vary depending on reaction conditions, thecatalyst employed, and the separation system that is used. In someexemplary embodiments, the enriched saturated hydrocarbon stream maycomprise the hydrocarbons in an amount greater than 40 weight percent,e.g., greater than 50 weight percent, greater than 60 weight percent orgreater than 75 weight percent, based on the total weight of theenriched saturated hydrocarbon stream. The enriched saturatedhydrocarbon stream may also comprise unreacted monomer in an amountgreater than 40 weight percent, e.g., greater than 50 weight percent,greater than 60 weight percent or greater than 75 weight percent, basedon the total weight of the enriched saturated hydrocarbon stream. Theenriched saturated hydrocarbon stream preferably comprises the PAO in anamount less than 5 weight percent, e.g., less than 2 weight percent orless than 1 weight percent, based on the total weight of the enrichedsaturated hydrocarbon stream. Conversely, the purified PAO productstream preferably comprises the hydrocarbons in an amount less than 1weight percent, e.g., less than 0.5 weight percent or less than 0.1weight percent, based on the total weight of the purified PAO productstream. The purified PAO product stream preferably comprises PAO in anamount greater than 97 weight percent, e.g., greater than 99 weightpercent or greater than 99.9 weight percent, based on the total weightof the purified PAO product stream.

Once separated, at least a portion of the enriched saturated hydrocarbonstream may be recycled to the reaction vessel as a recycle stream,optionally after being combined with the monomer feedstock. Additionalhydrocarbon (e.g., commercially available C₈-C₁₂ saturated hydrocarbon,preferably straight chain hydrocarbon) may be added to the recyclestream and/or to the monomer feedstock, if desired, to boost theconcentration of C₈-C₁₂ saturated hydrocarbon that is contained in thereaction vessel.

In this aspect, a portion of the enriched saturated hydrocarbon streampreferably is removed from the polymerization system as a purge streamto prevent the buildup of undesirable byproducts and contaminants. Thepurge stream preferably comprises on the order of from 5 to 35 weightpercent of the total enriched saturated hydrocarbon stream, e.g., from10 to 30 weight percent, or from 15 to 25 weight percent. In otherwords, from about 65 to 95 weight percent, e.g., from 70 to 90 weightpercent, or from 75 to 85 weight percent of the enriched saturatedhydrocarbon stream preferably is recycled to the reaction vessel.

In an alternative aspect, the saturated hydrocarbon, e.g., C₈-C₁₂saturated hydrocarbon or C₈-C₁₂ saturated straight-chain hydrocarbon, isco-fed to the reaction vessel with the monomer but is not derived fromthe crude PAO product. In this aspect, for example, the hydrocarbon maybe a commercially available saturated hydrocarbon, e.g., a saturatedhydrocarbon having a 50° C. vapor pressure within 20%, e.g., within 10%or within 5%, of the vapor pressure of the α-olefin.

In a hybrid aspect, during start up of the reaction vessel, thesaturated hydrocarbon initially may be co-fed to the reaction vesselwith the monomer but is not derived from the crude PAO product. Asindicated above, additional saturated hydrocarbons will be formed as abyproduct of the polymerization process. As the level of saturatedhydrocarbon byproducts formed in the reaction system increases and isseparated from the crude PAO product and recycled to the reactionvessel, the level of “fresh” hydrocarbon that is co-fed to the systemmay be gradually decreased until the system reaches a steady state.

As indicated above, additional saturated hydrocarbons, e.g., C₈-C₁₂saturated hydrocarbons, may also be formed as a byproduct of thepolymerization process of the invention, particularly since the monomeremployed will typically comprise a C₈-C₁₂ α-olefin monomer and thereaction is conducted in the presence of hydrogen. This should be takeninto consideration when determining the amount of “fresh” hydrocarbonthat is fed to the reaction vessel so that a desired saturatedhydrocarbon level is maintained in the reaction vessel. In someexemplary embodiments, the level of saturated hydrocarbons (e.g., theC₈-C₁₂ saturated hydrocarbon such as one or more decanes or thehydrocarbon having a 50° C. vapor pressure within 20%, e.g., within 10%or within 5%, of the α-olefin) is maintained in the reaction vessel at alevel of from 5 to 70 weight percent, e.g., from 8 to 40 weight percent,from 8 to 30 weight percent, or from 15 to 40 weight percent, based onthe combined weight of the α-olefin monomer (e.g., the C₈-C₁₂ α-olefinmonomer), saturated hydrocarbons and PAO in the reaction vessel.

Catalyst

The catalyst system used to produce the PAOs of the present inventionpreferably is formed by activating a metallocene procatalyst with asuitable co-catalyst. The metallocene procatalyst may be bridged orunbridged. Preferably, the metallocene procatalyst comprises one or amixture of metallocene compounds of the formula (I):

(Cp¹R¹ _(m))R³(Cp²R² _(p))MX_(q)   (I)

wherein Cp¹ of ligand (Cp¹R¹ _(m)) and Cp² of ligand (Cp²R² _(p)) arethe same or different cyclopendadienyl rings; R¹ and R² each is,independently, a hydrocarbyl, halocarbyl, heterocarbyl,hydrocarbyl-substituted organometalloid or halocarbylsubstitutedorganometalloid group containing up to 20 carbon atoms; m is an integerfrom 0 to 5; p is an integer from 0 to 5; two R¹ and/or R² substituentson adjacent carbon atoms of the cyclopentadienyl ring associatedtherewith can be joined together to form a ring fused to thecyclopentadienyl ring, the fused ring containing from 4 to 20 carbonatoms; R³ is a bridging group bridging Cp¹ and Cp²; M is a transitionmetal having a valence of from 3 to 6; each X is a non-cyclopentadienylligand and is, independently, halogen or a hydrocarbyl, oxyhydrocarbyl,halocarbyl, hydrocarbyl-substituted organometalloid,oxyhydrocarbyl-substituted organometalloid or halocarbyl-substitutedorganometalloid group containing up to 20 carbon atoms; and q is equalto the valence of M minus 2. Methods for preparing these and otheruseful metallocene procatalysts are known in the art. The catalystcomposition for use herein is preferably formed by activating ametallocene procatalyst with a suitable catalyst. The terms“metallocene” and “metallocene procatalyst” as used herein shall beunderstood to refer to compounds possessing a transition metal M, atleast one non-cyclopentadienyl-derived ligand X and zero or oneheteroatom-containing ligand Y, the ligand being coordinated to M andcorresponding in number to the valence thereof. Such compounds,cocatalysts useful for their activation to provide metallocene catalyststhat may be employed for the polymerization of olefins to providepolyolefin homopolymers and copolymers, and/or polymerization processesemploying one or more of the metallocene catalysts are described in,among others, U.S. Pat. Nos. 4,752,597; 4,892,851; 4,931,417; 4,931,517;4,933,403; 5,001,205; 5,017,714; 5,026,798; 5,034,549; 5,036,034;5,055,438; 5,064,802; 5,086,134; 5,087,677; 5,126,301; 5,126,303;5,132,262; 5,132,380; 5,132,381; 5,145,819; 5,153,157; 5,155,080;5,225,501; 5,227,478; 5,241,025; 5,243,002; 5,278,119; 5,278,265;5,281,679; 5,296,434; 5,304,614; 5,308,817; 5,324,800; 5,328,969;5,329,031; 5,330,948; 5,331,057; 5,349,032; 5,372,980; 5,374,753;5,385,877; 5,391,629; 5,391,789; 5,399,636; 5,401,817; 5,406,013;5,416,177; 5,416,178; 5,416,228; 5,427,991; 5,439,994; 5,441,920;5,442,020; 5,449,651; 5,453,410; 5,455,365; 5,455,366; 5,459,117;5,466,649; 5,470,811; 5,470,927; 5,477,895; 5,491,205; and, 5,491,207,the contents of which are incorporated by reference herein.

When employing the foregoing metallocene procatalyst and the cocatalystis entirely an aluminoxane, ligand (Cp¹R¹ _(m)) is preferably differentfrom ligand (Cp²R² _(p)), and bridging group R³ preferably contains atleast two bulky groups. Of these bridged metallocenes, it is preferredthat a bridging group R³ possess the structure:

wherein each of bulky groups R⁴ and R⁵, independently, is, or contains,a cyclohydrocarbyl group containing up to 20 and preferably from 6 to 12carbon atoms and from 0 to 3 heteroatoms such as oxygen, sulfur,tertiary nitrogen, boron or phosphorus and, in particular, is acycloalkyl, heterocycloalkyl, cycloalkenyl, heterocycloalkenyl, aryl,heteroaryl, alkaryl, alkylheteroaryl, aralkyl, heteroarallcyl, and thelike. M in the compound of formula (I) is titanium, zirconium orhafnium, q is 2 and each X is halogen.

Of this preferred group of bridged metallocenes, those in which ligand(Cp¹R_(m) ¹) is substituted or unsubstituted cyclopentadienyl, ligand(Cp²R_(p) ²) is indenyl or fluorenyl, M is zirconium, R⁴ and R⁵ each issubstituted or unsubstituted phenyl and each X ligand is chlorine areparticularly preferred.

Exemplary bridged metallocenes of the formula (I) that can be used inthe polymerization process of the embodiments of the present inventioninclude, without limitation: diphenylmethylene (indenyl) (fluorenyl)zirconium dichloride, diphenylmethylene (cyclopentadienyl)(4,5,6,7-tetrahydro-indenyl) zirconium dichloride, diphenylmethylene(cyclopentadienyl) (2-methylindenyl) zirconium dichloride,diphenylmethylene (2,4-dimethylcyclo-pentadienyl)(3′,5′dimethylcyclopentadienyl) zirconium dichloride,diphenylmethylene(2-methyl-4-tert-butylcyclo-pentadienyl)(3′-tert-butyl-5methylcyclopentadienyl) zirconium dichloride,dixylylmethylene (2,3,5-trimethylcyclopentadienyl)(2′,4,5′-trimethylcyclopentadienyl) zirconium dichloride,dixylylmethylene (2,4dimethylcyclopentadienyl)(3′,5′-dimethylcyclopentadienyl)zirconium dichloride, dixylylmethylene(2-methyl-4-tert-butylcyclopentadienyl)(3′-tert-butyl-5-methylcyclopentadienyl) zirconium dichloride,dixylylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,di-o-tolylmethylene (cyclopentadienyl) (3,4-dimethyl-cyclopentadienyl)zirconium dichloride, di-o-tolylmethylene (cyclopentadienyl)(3,4-dimethyl-cyclopentadienyl) zirconium dichloride,di-o-tolylmethylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl)zirconium dichloride, di-o-tolylmethylene (cyclopentadienyl) (indenyl)zirconium dichloride, dibenzylmethylene (cyclopentadienyl)(tetramethylcyclopentadienyl) zirconium dichloride, dibenzylmethylene(cyclopentadienyl) (indenyl) zirconium dichloride, dibenzylmethylene(cyclopentadienyl) (fluorenyl) zirconium dichloride,dicyclohexylmethylene (cyclopentadienyl) (indenyl) zirconium dichloride,dicyclohexyl (cyclopentadienyl) (fluorenyl) zirconium dichloride,dicyclohexylmethylene (2-methylcyclopentadienyl) (fluorenyl) zirconiumdichloride, diphenylsilyl(2,4-dimethylcyclopentadienyl)(3′,5-dimethylcyclopentadienyl) zirconiumdichloride, diphenylsilyl (2,4-dimethylcyclopentadienyl)(3′,5′-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilyl(2,3,5-trimethylcyclopentadienyl) (2,4,trimethylcyclopentadienyl)zirconium dichloride, tetraphenyldisilyl (cyclopentadienyl) (indenyl)zirconium dichloride, tetraphenyldisilyl (3-methylcyclopentadienyl)(indenyl) zirconium dichloride, tetraphenyldisilyl (cyclopentadienyl)(fluorenyl) zirconium dichloride, di-o-tolylsilyl (cyclopentadienyl)(trimethylcyclopentadienyl) zirconium dichloride, di-o-tolylsilyl(cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride,di-o-tolylsilyl (cyclopentadienyl) (3,4-diethylcyclopentadienyl)zirconium dichloride, di-o-tolylsilyl (cyclopentadienyl)(triethylcyclopentadienyl) zirconium dichloride, dibenzylsilyl(cyclopentadienyl) (fluorenyl) zirconium dichloride, dibenzylsilyl(cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) zirconium dichloride,dicyclohexylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride,and diphenylmethylene (cyclopentadienyl-9-fluorenyl)zirconiumdichloride.

In a preferred embodiment, the polymerizing occurs in the presence of acatalyst having the formula Ph₂C(Cp-9-Flu)ZrCl₂ (diphenylmethylene(cyclopentadienyl-9-fluorenyl)zirconium dichloride, also referred toherein as CpFlu), which is represented by the following structure.

The cocatalyst, or activator, employed with the metallocene procatalystsof formula (I) can be any of the aluminoxanes known to activatemetallocene procatalysts. Exemplary aluminoxane cocatalysts includealkylaluminoxanes such as methylaluminoxane (MAO). See, e.g., U.S. Pat.No. 5,229,478, the entirety of which is incorporated by reference as iffully set forth herein.

In general, the bridged metallocene procatalyst can be present in thereaction vessel in an amount, expressed in terms of its transition metalcontent, of from 0.0001 mmol/L to 5 mmol/L, e.g., from 0.0001 mmol/L to0.09 mmol/L, from 0.001 to mmol/L to 0.05 mmol/L, 0.002 mmol/L to 0.05mmol/L, 0.01 to mmol/L to 0.05 mmol/L, from 0.015 mmol/L to 0.03 mmol/L,and preferably about 0.025 mmol/L.

Corresponding to these amounts of transition metal, the aluminoxanecocatalyst can be utilized in an amount in the reaction vessel of fromabout 0.002 mmol/L to about 50 mmol/L, preferably from about 0.002mmol/L to about 25 mmol/L and more preferably from about 0.02 mmol/L toabout 10 mmol/L. The optimum levels of bridged metallocene procatalystand aluminoxane cocatalyst will, to some extent, depend upon thespecific procatalyst and cocatalyst selected as well as otherpolymerization process variables.

In terms of levels of aluminoxane cocatalyst to metallocene procatalystin the reaction vessel, the molar ratios can be, for example, about1000:1, about 750:1, about 500:1, about 250:1, about 100:1, about 50:1,or about 25:1. In some embodiments, the level of metallocene procatalystto aluminoxane cocatalyst is preferably 500:1. In other embodiments, thelevel of metallocene procatalyst to aluminoxane cocatalyst is preferably100:1. In still other embodiments, the level of metallocene procatalystto aluminoxane cocatalyst is preferably 25:1. In terms of ranges, themolar ratio of the aluminoxane cocatalyst to the metallocene catalystoptionally is from 25:1 to 3000:1, e.g., 25:1 to 1000:1, or 250:1 to1000:1. When C₈-C₁₂ saturated hydrocarbons and/or hydrocarbons having avapor pressure within 20% of the α-olefin are fed to the reactionsystem, the preferred molar ratio of aluminoxane cocatalyst tometallocene catalyst is from about 50:1 to about 1000:1, e.g., fromabout 200:1 to about 800:1, and most preferably about 300:1. Higherratios are generally desired for polymerization reaction systems inwhich hydrocarbons are not fed to the reaction system.

When employing an aluminoxane cocatalyst, it can be advantageous toinclude a trialkylaluminum compound such as trimethylaluminum,triethylaluminum, tri(n-propyl)aluminum, triisopropyaluminum,tri(n-butyl)aluminum, triisobutylaluminum, and the like, to reduce theamount of aluminoxane required for suitable activation of themetallocene procatalyst. In general, the optional trialkylaluminum canbe utilized in a molar level to metallocene procatalyst of from about 1to about 1000 and preferably from about 2 to about 500.

It is also contemplated that a neutral or anionic metalloid-containingcomponent can optionally be employed with the aluminoxane cocatalyst inactivating the metallocene procatalyst. Exemplary neutralmetalloid-containing components include boranes such asperfluoroarylborane compounds, e. g., tris(pentafluorophenyl)borane,tris(methoxyphenyl)borane, tris(trifluoromethylphenyl)borane, tris(3,5-di[trifluoro-methyl]phenyl)borane, tris(tetrafluoroxylyl)borane,tris(tetrafluoro-o-tolyl)borane, and the like. Of the foregoing boranes,tris(pentafluorophenyl)borane and tris (3,5di[trifluoromethyl]phenyl)borane are preferred. Other useful second components include aluminumhomologues of the foregoing compounds.

Exemplary anionic metalloid-containing components include borates suchas perfluoroaryl borates, e. g., lithiumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(trifluoromethylphenyl)borate, lithiumtetrakis(3,5-di[tri-fluoromethyl]phenyl)borate, sodiumtetrakis(pentafluoro-phenyl)borate, potassiumtetrakis(pentafluorophenyl)borate, magnesiumtetrakis(pentafluorophenyl)borate, titaniumtetrakis(pentafluorophenyl)borate, tintetrakis(pentafluorophenyl)borate, dimethylaniliniumtetrakis(pentafluorophenyl)borate and the like. Of the foregoingborates, dimethylaniliniumtetrakis (pentafluorophenyl) borate and alkalimetal borates such as lithium tetrakis(pentafluorophenyl)borate andlithium tetrakis (3,5-di[trifluoro-methyl]phenyl)borate are preferred.In some embodiments, aluminate homologues of the foregoing compounds maybe used.

In general, neutral or anionic metalloid-containing components can beutilized in a molar level to metallocene procatalyst of about 1:2, about1:1.5, about 1:1, or about 1:0.5. When the anionic metalloid-containingcomponent is dimethylaniliniumtetrakis(pentafluorophenyl)borate, thelevel of the borate to the metallocene procatalyst is 1:1.

Activation of the metallocene to yield an activated metallocene catalystcomposition can be achieved by combining the aforementioned metalloceneprocatalysts with the aluminoxane cocatalyst, optionally in the presenceof a neutral or anionic metalloid-containing component, eithersimultaneously or in any sequence and with any interval of timetherebetween and either in the presence of, or in the absence of, theolefin monomer(s) and hydrogen. The activation optionally occurs at atemperature ranging from 0 to 100° C., and optionally for a time periodranging from 1 minute to 72 hrs. Optionally, activation occurs in from 0to 99% of an inert hydrocarbon solvent, either aliphatic or aromatic. Ina preferred embodiment, the metallocene catalyst is activated for 10minutes at room temperature and with toluene as solvent.

In some embodiments, the activated metallocene catalyst compositions isprepared in advance and thereafter the composition is introduced intothe polymerization reactor with the olefin monomer (s), optionally inthe presence of hydrogen.

The reaction of the metallocene procatalyst with the aluminoxanecocatalyst to generate an activated metallocene catalyst preferably isconducted at a temperature ranging from about 0 to about 100° C., e.g.,from about 0 to about 80° C., from about 10 to about 50° C., about 25 toabout 50° C.; for a time period of from about 1 minute to about 72hours, e.g. from about 1 minute to about 50 hours, from about 1 minuteto about 30 hours, or from about 1 minute to about 24 hours.

Process Parameters

The polymerization processes of the invention may be carried out in anyknown manner, e.g., in the liquid phase, i.e., in a solution or slurryprocess, or in a suspension process, either continuously,semi-continuously, or in batch. These processes are generally carriedout at temperatures in the range of from about 105° C. to about 170° C.,preferably from 110° C. to 150° C., from 120° C. to 140° C., andpreferably about 130° C. (lower temperatures are generally desired forpolymerization reaction processes). The pressure within the reactionvessel optionally ranges from 0 to 3000 psig (0 to 20700 kPag), e.g.,from 0 to 600 psig (0 to 4100 kPag) or from 10 to 240 psig (70 to 1700kPag). Other preferred pressures range from 0 to 4240 kPag, e.g., 1.7 to1760 kPag or from 520 to 720 kPag. Pressures greater than 1500 kPag aregenerally desired for conventional polymerization reaction processes. Asone skilled in the art would readily appreciate, control of thepolymerization temperature has a direct bearing on the quality of thepolymerization, e.g., activity, as well as the final product properties,e.g., Iodine Number. However, as these temperatures approach 150° C. orgreater, the exothermic temperature, i.e., the maximum temperaturereached during the polymerization, should be substantially close to theinitial polymerization temperature, e.g., at temperatures above about150° C. the exothermic temperature should be no more than about 20° C.greater than the initial polymerization temperature.

The polymerization can be carried out in liquid monomer and in theabsence of solvent or, if desired, in the presence of solvent. In thiscontext, the term “solvent” refers to a non-reactive liquid other thanthe C₈-C₁₂ saturated hydrocarbon of the first embodiment or thehydrocarbon of the second embodiment. Dilution solvents that can beemployed include straight and branched chain hydrocarbons, such asbutanes, pentanes, hexanes, heptanes, and the like, cyclic and alicyclichydrocarbons, such as cyclopentane, cyclohexane, cycloheptane,methyl-cyclopentane, methylcyclohexane, methylcycloheptane, and thelike, and alkyl-substituted aromatic compounds, such as toluene, xylene,and the like, and mixtures of the foregoing.

Preferably, the polymerization process is a continuous orsemi-continuous polymerization reaction process, meaning that monomer iscontinuously or semi-continuously fed to the reaction vessel and productis continuously or semi-continuously removed from the reaction vessel.This aspect of the invention is described in greater detail below withreference to FIGS. 1-3. In these aspects, the PAO preferably has aresidence time in the reaction vessel on the order of from 5 to 300minutes, e.g., 10 to 60 minutes, 15 to 45 minutes, or 20 to 40 minutes.

Surprisingly and unexpectedly, it has been discovered that the residencetime of the PAO in the reaction vessel has an inverse impact on theviscosity of the resulting PAO that is formed. Specifically, it has beendiscovered that when the reaction system is operated at greaterresidence times, the kinematic viscosity of the resulting PAO is reducedrelative to PAO formed at lower residence times. Thus, in the fifthembodiment, the invention is to a process for forming a PAO in which thekinematic viscosity of the PAO is controlled based on the residence timeof the PAO in the reaction vessel. The process comprises the step ofpolymerizing in a reaction vessel a C₈-C₁₂ α-olefin in the presence ofhydrogen, and a catalytically effective amount of a catalyst systemunder conditions effective to form the PAO, wherein the PAO has anaverage residence time in the reaction vessel of greater than 5 minutes,and the PAO has a kinematic viscosity of no more than 200 cSt. In apreferred embodiment, the PAO has an average residence time in thereaction vessel of greater than 10 minutes, and the PAO has a kinematicviscosity of no more than 150 cSt. In an even more preferred embodiment,the PAO has an average residence time in the reaction vessel of greaterthan 25 minutes, and the PAO has a kinematic viscosity of no more than125 cSt.

In another embodiment, the process is a batch polymerization process. Atypical batch solution polymerization process can be carried out byfirst introducing the α-olefin monomer, e.g., a C₈-C₁₂ α-olefin monomersuch as 1-decene, either alone or in combination with an optionalhydrocarbon solvent, e.g., hexanes, xylenes, etc., into a stirred tankreactor. The C₈-C₁₂ saturated hydrocarbon of the first embodiment, e.g.,one or more decanes, or the hydrocarbon of the second embodiment (havinga 50° C. vapor pressure within 20%, e.g., within 10% or within 5%, ofthe vapor pressure of the pure α-olefin monomer) can be fed eithersequentially or simultaneously with the α-olefin monomer. A minor amountof an inert impurity scavenger, e.g., the aforementionedtrialkylaluminum compounds, can also be fed at this time. The reactor isthen brought up to the desired temperature, e.g., from about 0° C. toabout 200° C., from about 50° C. to about 150° C., or from 80° C. to140° C., and a measured amount of hydrogen can then be introduced intothe stirred tank reactor. If copolymerization is desired with a gaseousmonomer, a minor monomer feed comprising the minor monomer, for example,ethylene or 1-propene, may be sparged into the liquid phase, either incombination with, or separate from the hydrogen feed.

Once the desired conditions are established, a hydrocarbon solution ofthe catalyst in the required amount is then fed to the liquid phase inthe reactor. In this aspect, the hydrocarbon solution optionallycomprises the C₈-C₁₂ saturated hydrocarbon of the first embodiment orthe hydrocarbon of the second embodiment. In another aspect, thehydrocarbon solution comprises toluene. Although high levels of toluenemay result in decreased selectivity, a small amount of toluene, e.g.,less than 7 weight percent, less than 5 weight percent, less than 2weight percent or less than 1 weight percent toluene, based on the totalweight of the feedstock, has been found to be generally tolerable in thepolymerization reaction processes of the present invention. Otheraliphatic and aromatic solvents, such as a xylene and benzene, may havea similar effect on selectivity. The rate of polymerization iscontrolled, among other factors, by the concentration of the catalystand monomers present or fed during polymerization. The reactortemperature is preferably controlled by means of cooling coils,agitation, etc., and the initial total pressure in the reactor may bemaintained by a constant flow of hydrogen, inert gas, gaseous monomersor a combination thereof. After polymerization is complete, the reactoris depressurized and the catalyst is deactivated by conventional means.

Depending on the amount of monomer conversion and viscosity of thereactor contents, a hydrocarbon solvent (in addition to the C₈-C₁₂saturated hydrocarbon of the first embodiment or the hydrocarbon of thesecond embodiment) can be added to aid in removing the productpolyolefin from the reactor. Spent catalyst components can be isolatedfrom the reaction product via mixing with, e.g., alcohol, water, or amixture of both, and then by phase separation of the hydrocarbylcomponent from the aqueous component. The liquid PAO can then berecovered from the hydrocarbyl component by conventional methods, e.g.,evaporation, distillation, etc., and then further processed as desired.

Since water, even in small amounts, is highly undesirable in thepolymerization reaction vessel, in those embodiments of the invention inwhich the C₈-C₁₂ saturated hydrocarbon of the first embodiment or thehydrocarbon of the second embodiment is derived from the crude PAOproduct and recycled to the reaction vessel, as described above, thespent catalyst components preferably are not isolated via mixing with anaqueous phase. Instead, for example, the spent catalyst (e.g.,metallocene catalyst, co-catalyst and optional activator) may beseparated from the crude PAO product stream by contacting the crude PAOproduct stream, which contains the spent catalyst, with one or moresolid adsorbent materials capable of selectively adsorbing the catalystthereto.

The contacting preferably occurs in a catalyst removalcolumn—particularly when the polymerization process is a continuous orsemi-continuous process. The catalyst removal column preferably ispacked with the solid adsorbent material. The crude PAO product streammay be allowed to flow in an upward direction or a downward direction,at an angle, or in a horizontal direction. A non-limiting list ofexemplary solid adsorbent materials includes acidic clay, zeolites,calcium oxide, magnesium oxide, silicates and mixtures thereof. Othermetal oxides may also be used. The solid adsorbent material may have avolume average particle size (diameter for generally sphericalparticles) ranging, for example, from 50 μm to 2 cm, e.g., from 100 μmto 1 cm, or from 250 μm to 1000 μm, and a bulk density that maintains areasonable pressure drop (e.g., <200 psi (<1379 kPa)). The recycle ofsaturated hydrocarbon to the reaction vessel is highly desirable inthose embodiments of the invention that employ a catalyst removal columnbecause the saturated hydrocarbon reduces the viscosity of the crude PAOproduct stream such that the crude PAO product is capable of passingthrough the solid adsorbent material. In the absence of the saturatedhydrocarbon recycle (or the presence of an alternative solvent system),the high viscosity of the resulting PAO product stream may preclude theuse of the inventive catalyst removal column. Thus, the saturatedhydrocarbon recycle preferably is employed together with the inventivecatalyst removal column.

The amount of solid adsorbent contained in the column will varydepending, for example, on the adsorbent used, particle size anddistribution, and the flow rate. In some exemplary embodiments, theweight ratio of adsorbent employed to PAO to be processed ranges from0.005:1 to 0.5:1, e.g., from 0.01:1 to 0.25:1, or from 0.01:1 to 0.1:1,and most preferably is about 0.05:1. The temperature of the column mayrange, for example, from about room temperature to about 125° C. orhigher.

As the catalyst removal column is used, the flow rate of the PAO productstream through the column gradually will tend to slow. Accordingly, thepressure of the PAO to the column may be gradually increased to offsetthe gradual plugging of the column. The PAO pressure to the column mayrange, for example, from about 10 psig (172 kPag) for a fresh column toabout 200 psig (1379 kPag) for a more used column, e.g., from about 25psig (172 kPag) to about 200 psig (1379 kPag) or from about 100 psig(689 kPag) to about 200 psig (1379 kPag). At some point, it may benecessary to temporarily stop the flow of catalyst to the column inorder to allow the spent adsorbent to be replaced with fresh adsorbent.The spent adsorbent may be disposed of or regenerated and reused.

For batch processes, the solid adsorbent material may be added directlyto the crude PAO product, e.g., as a powder, and then filtered to removethe solid adsorbent material and the catalyst that is adsorbed thereonand thereby form a reduced catalyst PAO stream.

As indicated above, the processes of the present invention preferablyprovide significantly improved selectivity and yield over conventionalPAO synthesis processes, while maintaining high conversion. For example,the overall conversion of the polymerization processes of the presentinvention may be greater than 85 percent, e.g., greater than 90 percent,greater than 95 percent or greater than 99 percent. Conversion refers toamount of α-olefins that are converted during the polymerization processto saturated monomers, PAO, or any other byproducts. Conversionpercentage is calculated by dividing the weight of the α-olefins reactedby the weight of the α-olefins fed to the system. Selectivity, accordingto the processes of the invention, preferably is maintained at a highlevel, e.g., at least 90 percent, at least 95 percent, at least 97percent or at least 99 percent. As used herein, “selectivity” refers tothe percent of converted α-olefins that are converted to PAO (on aweight basis). A higher selectivity indicates a higher production of thedesired PAO relative to non-PAO products. Similarly, the overall yieldfor the polymerization processes of the present invention may, forexample, be greater than 75 percent, e.g., greater than 80 percent,greater than 85 percent, greater than 90 percent or greater than 95percent. Yield percentage is calculated by multiplying conversion byselectivity. In one embodiment, the selectivity is greater than 90percent, the yield is greater that 75 percent and the conversion isgreater than 85 percent. In still other embodiments, a PAO produced bythe present invention may have the percentages defined by anycombination of the above-identified ranges for selectivity, yield andconversion.

Polyalphaolefins and Applications

The PAO polymers that can be obtained by the polymerization processesdescribed herein are preferably substantially amorphous. In addition tobeing substantially amorphous, the PAO polymers that can be obtained bythe polymerization process herein possess a unique combination of lowweight average molecular weight (M_(w)), low polydispersity index(M_(w)/M_(n), where M_(n) is number average molecular weight),controllable kinematic viscosity (Kv₁₀₀), high viscosity index (VI), lowIodine Number (I₂#), i.e., a substantially saturated PAO, and low glasstransition temperature (T_(g)) that distinguish them from known PAOs.The novel PAO polymers possess a M_(w) of from about 500 to about80,000, e.g., from about 750 to about 60,000, from about 1,000 to about40,000, from about 1,000 to about 10,000, or from about 2,500 to about7,500, a M_(w)/M_(n) of from about 1.0 to about 10, preferably fromabout 1.5 to about 5, more preferably from about 1.75 to about 4, anIodine Number of from about 0.0 to about 10, preferably from about 0.1to about 5, more preferably from about 0.2 to about 3, and a T_(g) ofbelow about −20° C., preferably below about −30° C., more preferablybelow about −40° C. Unless otherwise specified, molecular weightsprovided herein are determined through gel permeation chromatographyusing polystyrene standards.

The PAO formed by the processes of the present invention preferably hasa particularly low kinematic viscosity. In various exemplaryembodiments, the Kv₁₀₀ may range from about 10 to about 10,000 cSt,e.g., from about 20 to about 7,500 cSt, or from about 25 to about 5,000cSt. In more preferred aspects, the Kv₁₀₀ may range from 50 to 500 cSt,e.g., from 50 to 150 cSt, from 90 to 120 cSt or from 95 to 115 cSt.Unless otherwise indicated, kinematic viscosity is determined accordingto ASTM D-445, the entirety of which is incorporated herein byreference. The PAO preferably has a VI ranging from 120 to 500, e.g.,from 170 to 200, as determined by ASTM D-2270, the entirety of which isincorporated herein by reference.

These advantageous properties can be exploited in a variety of productssuch as, for example, products which require a viscous oil or an inertmaterial with fluid properties such as dispersants, heat transferfluids, cosmetics, or other such consumer products, and the like.

In one embodiment, the PAO structure has a predominately head-to-tailconfiguration, where 70% or more of the α-olefin monomers are joined ina head to tail manner, e.g. 80% or more or 90% or more. A head-to-tailconfiguration is the result of a 1-2 addition, where the first carbonatom of a first monomer (head) is bonded to the second carbon in asecond monomer (tail). In one embodiment, the PAO structure has a lowhead-to-head or tail-to-tail configuration where less than 30% of themonomers are either head-to-head or tail-to-tail, e.g. less than 20% orless than 10%. The predominately head-to-tail configuration of PAOsproduced by the present invention may have a peak in the region of 41-40ppm in a ¹³C Nuclear Magnetic Resonance (NMR) analysis. In addition, alow head-to-head configuration may have no discernible peak in theregion of 42.5 ppm and a low tail-to-tail configuration may have nodiscernible peak in the region of 21-20 ppm. By “no discernible peak” itis meant that that the relative content or peak integral in therespective region is less than 1.0%, e.g. less than 0.5% or less than0.1 of the total peak integral. A low head-to-head or tail-to-tailconfiguration indicates that there are few misinsertions orrearrangements in the PAO structure. In one embodiment the lowhead-to-head or tail-to-tail configuration indicates that there are nomisinsertions or rearrangements in the PAO structure.

In addition to a predominately head-to-tail configuration, PAOs of thepresent invention typically have low isotacticity. Isotacticity may bedetermined using ¹³C NMR analysis based on the relative content or peakintegral in a region that corresponds to mm triads. The relative contentof isotactic structure is equivalent to the mole percent of mm triads.The region of mm triads is from 35.50 to 34.96 ppm, and the region mayinclude one or more pentads such as mmmm, mmmr, or rmmr. A lowisotacticity PAO in accordance with an embodiment of the presentinvention has a mole % of mm triads of from 0.5 to 5.0, e.g., from 1.0to 4.0, or from 1.5 to 3.0.

In addition to a predominately head-to-tail configuration, PAOs of thepresent invention typically have a very high degree of syndiotacticity.Syndiotacticity may be determined using ¹³C NMR analysis by the relativecontent or peak integral in a region that corresponds to rr triads. Therelative content of syndiotactic structure is equivalent to the molepercent of rr triads. The region of rr triads is from 34.40 to 33.71ppm, and the region may include one or more pentads such as rrrr, rrrm,or mrrm. The syndiotacticity of a PAO in accordance with an embodimentof the present invention has a mole % of rr triads from 40.0 to 58.0,e.g., from 42.0 to 55.0, or from 46.0 to 52.0 mole %.

PAOs of the present invention also may be atactic or heterotactic inaddition to having a predominant head-to-tail configuration. Atacticitymay be determined by the relative content of a region using ¹³C NMRanalysis that corresponds to mr triads. The relative content of atacticstructure is equivalent to the mole percent of mr triads. The region ofmr triads is from 34.96 to 34.40 ppm, and the region may include one ormore pentads such as mmrr, mmrm, rmrr or rmrm. The atacticity of a PAOin accordance with an embodiment of the present invention has a mole %of mr triads from 37.0 to 59.5, e.g., from 40.0 to 55.0 mole % or from45.0 to 50.0 mole %.

In one embodiment, the PAO structure may have the following tacticities:0.5 to 5.0 mole % of mm triads and 40.0 to 58.0 mole % of rr triads. Inanother embodiment, the PAO structure may have the followingtacticities: 0.5 to 5.0 mole % of mm triads, 40.0 to 58.0 mole % of rrtriads and 37.0 to 59.5 mole % of mr triads. In still anotherembodiment, a PAO produced by the present invention may have tacticitiesdefined by any combination of the above-identified ranges for mm, mr orrr triads.

Additionally, the products of this invention can be used in graftingapplications to produce functionalized low molecular weight polymers.The PAO polymers of this invention are particularly useful as viscositymodifiers for lubricants, especially lubricating oils, wherein thepolymer is employed in a viscosity-modifying amount. Concentrations offrom about 1 to about 99 weight percent based on the total weight of thelubricant composition can be used. Preferably, the concentration is fromabout 5 to about 85 weight percent.

In general, mineral oils, both paraffinic, naphthenic and mixturesthereof, including those oils defined as American Petroleum InstituteGroups I, II, and III can be employed as the lubricant vehicle, and canbe any suitable lubricating viscosity range, as, for example, from about2 cSt at 100° C. to about 1,000 cSt at 100° C., preferably from about 2to about 100 cSt at 100° C. These oils can have viscosity indicespreferably ranging to about 180. The average molecular weights of theseoils can range from about 250 to about 800.

Where synthetic oils are employed, they can include, but are not limitedto, polyisobutylene, polybutenes, hydrogenated polydecenes,polypropylene glycol, polyethylene glycol, trimethylpropane esters,neopentyl and pentaerythritol esters, di(2-ethylhexyl)sebacate,di(2-ethylhexyl)adipate, dibutyl phthalate, fluorocarbons, silicateesters, silanes, esters of phosphorus-containing acids, liquid ureas,ferrocene derivatives, hydrogenated synthetic oils, chain-typepolyphenyls, siloxanes and silicones (polysiloxanes), alkylsubstituteddiphenyl ethers typified by a butyl-substituted bis(p-phenoxy phenyl)ether, and phenoxy phenylethers.

The lubricant compositions can also contain one or more other materials,for example, detergents, corrosion inhibitors, oxidative inhibitors,dispersants, pour point dispersants, anti-foaming agents, anti-wearagents, other viscosity modifiers, friction modifiers, and the like atthe usual levels in accordance with well known practice. Othermaterials, including extreme pressure agents, low temperature propertiesmodifiers, and the like, can also be used, as exemplified, respectively,by metallic phenates or sulfonates, polymeric succinimides, non-metallicor metallic phosphorodithioates, and the like, at the usual levels inaccordance with well known practice. These materials do not detract fromthe value of the compositions of this invention, but rather serve toimpart their customary properties to the particular compositions inwhich they are incorporated.

In one aspect, the low viscosity PAOs of the invention may be blendedwith one or more higher viscosity materials as described, for example,in U.S. Publ. Pat. Appl. Nos. US 2006/0276355 A1, US 2007/0298990 A1, US2007/0289897 A1, US 2008/0020954 A1, and WO 2007/145924 A1 and WO2007/146081, the entireties of which are incorporated herein byreference.

Reaction System

In another embodiment, the invention is to a reaction system forperforming the above-described processes of the present invention. FIG.1 illustrates a flow diagram of an exemplary reaction system 100according to one aspect of the second embodiment of the invention. Asshown, reaction system 100 comprises a reaction vessel 101, a catalystremoval unit 102, and a separation zone 103.

As shown, monomer-containing feedstock 104, hydrogen feedstock 106 andcatalyst feed 105, are directed to reaction vessel 101. Themonomer-containing feedstock 104 comprises an α-olefin (e.g., a C₈-C₁₂α-olefin monomer such as 1-decene), a hydrocarbon (e.g., a C₈-C₁₂saturated hydrocarbon such as one or more decanes or a hydrocarbonhaving a 50° C. vapor pressure within 20%, e.g., within 10% or within5%, of the α-olefin), optionally one or more minor monomers andoptionally a solvent. In this embodiment, the hydrocarbon may, forexample, be a commercially available hydrocarbon. As indicated above,the hydrocarbon preferably has the same number of carbon atoms as theα-olefin. The catalyst feed 105 comprises a catalyst system, whichpreferably comprises a polymerization catalyst (preferably a metalloceneprocatalyst), a suitable co-catalyst (preferably an aluminoxane such asMAO), and optionally an anionic metalloid-containing component (e.g., aborane or a borate), as described above. The catalyst feed 105 may alsoinclude a catalyst solvent, such as toluene. Hydrogen feedstock 106comprises hydrogen gas. Hydrogen feedstock 106 may, for example, besparged into reaction system 100. In another embodiment, not shown, thehydrogen may be added (e.g., bubbled or sparged) to themonomer-containing feedstock 104, which is then directed to reactionvessel 101. Reaction vessel 101 also preferably includes a vent line,not shown, for venting gaseous components therefrom.

In reaction vessel 101, the monomers contact the polymerizationcatalyst, the hydrocarbon, and the hydrogen under conditions effectiveto form the PAO, preferably a highly saturated PAO. The crude PAOproduct is yielded from the reaction vessel 101 via crude PAO stream107, and directed to a catalyst separation unit 102. As shown, thecatalyst separation unit comprises a catalyst removal column, whichpreferably is packed with one or more materials capable of deactivatingthe catalyst and preferably capable of selectively separating thecatalyst from the crude PAO product to form a reduced catalyst PAOstream 108, which is directed to separation zone 103.

Separation zone 103 comprises one or more separation units, e.g., flashvessels, evaporators, strippers, distillation columns, etc., capable ofseparating the PAO product from the other components contained inreduced catalyst PAO stream 108. As shown, separation zone 103 separatesthe reduced catalyst PAO stream 108 into one or more byproduct streams109 (one is shown) and a purified PAO product stream 110.

In another aspect, as discussed above, hydrocarbons are separated fromthe crude PAO product and recycled to the reaction vessel. FIG. 2provides a flow diagram of an exemplary reaction system 200 according tothis aspect of the invention. As shown, reaction system 200 comprises areaction vessel 201, a catalyst removal unit 202, and a separation zone203. As shown, separation zone 203 comprises a flash vessel 211 and aseparation unit 212.

As shown, an initial monomer-containing feedstock 213 is combined with arecycle stream 220 comprising a hydrocarbon, e.g., a C₈-C₁₂ saturatedhydrocarbon, to form combined monomer-containing feedstock 204. Recyclestream 220 also may comprise unreacted monomer. Combinedmonomer-containing feedstock 204, hydrogen feedstock 206 and catalystfeed 205 are directed to reaction vessel 201. The combinedmonomer-containing feedstock 204 comprises an α-olefin (e.g., a C₈-C₁₂α-olefin such as 1-decene), a hydrocarbon (e.g., a C₈-C₁₂ saturatedhydrocarbon such as one or more decanes or a hydrocarbon having a 50° C.vapor pressure within 20%, e.g., within 10% or within 5%, of theα-olefin) derived from the crude PAO product, optionally one or moreminor monomers and optionally a solvent. As indicated above, thehydrocarbon preferably has the same number of carbon atoms as theα-olefin. The catalyst feed 205 comprises a catalyst system, whichpreferably comprises a polymerization catalyst (preferably a metalloceneprocatalyst), a suitable co-catalyst (preferably an aluminoxane such asMAO), and optionally an anionic metalloid-containing component (e.g., aborane or a borate), as described above. The catalyst feed 205 may alsoinclude a catalyst solvent, such as toluene. Hydrogen feedstock 206comprises hydrogen gas. In another embodiment, not shown, the hydrogenmay be added to the monomer-containing feedstock 204, which is thendirected to reaction vessel 201. Reaction vessel 201 also preferablyincludes a vent line, not shown, for venting gaseous componentstherefrom.

In reaction vessel 201, the α-olefin contacts the polymerizationcatalyst, the hydrocarbon, and the hydrogen under conditions effectiveto form the PAO, preferably a highly saturated PAO. Crude PAO product isyielded from the reaction vessel 201 via crude PAO stream 207 and isdirected to a catalyst separation unit 202. As shown, the catalystseparation unit comprises a catalyst removal column, which preferably ispacked with one or more materials capable of deactivating the catalystand preferably separating the catalyst from the crude PAO product toform a reduced catalyst PAO stream 208, which is directed to separationzone 203.

In FIG. 2, separation zone 203 comprises flash vessel 211 and one ormore separation units 212 (one is shown), e.g., flash vessels,evaporators, and/or distillation columns, and preferably is capable ofefficiently separating the PAO product from the other componentscontained in reduced catalyst PAO stream 208. Separation zone 203 alsopreferably is capable of efficiently separating a weight majority of thehydrocarbon, e.g., a decane, from reduced catalyst PAO stream 208. Asshown, separation zone 203 separates the reduced catalyst PAO stream 208into first stage overhead stream 214, second stage overhead stream 216,and purified PAO product stream 210.

In the embodiment shown, reduced catalyst PAO stream 208 is directed toflash vessel 211, where a rough separation is made between the PAOproduct formed in the reaction process and the light components (e.g.,unreacted monomer, the hydrocarbon and catalyst solvent) contained inreduced catalyst PAO stream 208. Specifically, flash vessel 211 formsfirst overhead stream 214 and first bottoms stream 215. First overheadstream 214 preferably comprises a weight majority, e.g., at least 80weight percent, at least 95 weight percent, at least 98 weight percentor at least 99 weight percent of the hydrocarbons (e.g., the C₈-C₁₂saturated hydrocarbon such as one or more decanes or a hydrocarbonhaving a 50° C. vapor pressure within 20%, e.g., within 10% or within5%, of the α-olefin) contained in the reduced catalyst PAO stream 208.First overhead stream 214 also preferably comprises a weight majority,e.g., at least 80 weight percent, at least 95 weight percent, at least98 weight percent or at least 99 weight percent of the unreacted monomercontained in the reduced catalyst PAO stream 208. If the catalyst fromcatalyst feed 205 contained a catalyst solvent, e.g., toluene, then thefirst overhead stream 214 may also comprise a weight majority, e.g., atleast 80 weight percent, at least 95 weight percent, at least 98 weightpercent or at least 99 weight percent of the catalyst solvent containedin the reduced catalyst PAO stream 208. First bottoms stream 215preferably comprises a weight majority, e.g., at least 80 weightpercent, at least 95 weight percent, at least 98 weight percent or atleast 99 weight percent of the PAO contained in the reduced catalyst PAOstream 208. Preferably, first overhead stream 214 is separated into afirst aliquot portion 217 and a second aliquot portion 218. Secondaliquot portion 218 is removed from the reaction system 200 as a purgestream in order to avoid the undesirable build up of light contaminantsin the reaction system.

First bottoms stream 215 is then directed to separation unit 212, wherea second separation is made between the PAO product and any lightcomponents (e.g., unreacted monomer, the hydrocarbons and catalystsolvent) contained in first bottoms stream 215. Specifically, separationunit 212 forms second overhead stream 216 and purified PAO productstream 210. Second overhead stream 216 preferably comprises a weightmajority, e.g., at least 80 weight percent, at least 95 weight percent,at least 98 weight percent or at least 99 weight percent of thehydrocarbon (e.g., the C₈-C₁₂ saturated hydrocarbon such as one or moredecanes or the hydrocarbon having a 50° C. vapor pressure within 20%,e.g., within 10% or within 5%, of the α-olefin) contained in the firstbottoms stream 215. As described above with reference to first overheadstream 214, an aliquot portion, not shown, of second overhead stream 216may be removed from the reaction system 200 as a purge stream. PurifiedPAO product stream 210 preferably comprises a weight majority, e.g., atleast 80 weight percent, at least 95 weight percent, at least 98 weightpercent or at least 99 weight percent of the PAO contained in the firstbottoms stream 215. Ideally, purified PAO product stream 210 comprisessubstantially pure PAO product.

In the embodiment of FIG. 2, the first aliquot portion 217 of firstoverhead stream 214 is combined with second overhead stream 216 to formrecycle stream 220, which is added to initial monomer-containing stream213 to form combined monomer-containing feedstock 204. In this manner,hydrocarbons and unreacted monomer from first overhead stream 214 andsecond overhead stream 216 are recycled to reaction vessel 201,surprisingly and unexpectedly resulting in improved overall selectivityand yield.

In another aspect, additional separation steps are employed in order toremove undesirable light components, e.g., catalyst solvent, from thecrude PAO product, while recycling the hydrocarbon (e.g., the C₈-C₁₂saturated hydrocarbon such as one or more decanes or a hydrocarbonhaving a 50° C. vapor pressure within 20%, e.g., within 10% or within5%, of the α-olefin) from the crude PAO product to the reaction vessel.FIG. 3 provides a flow diagram an exemplary reaction system 300according to this aspect of the invention. As shown, reaction system 300comprises a reaction vessel 301, a catalyst removal unit 302, and aseparation zone 303. As shown, separation zone 303 comprises a firstflash vessel 321, a second flash vessel 311 and a separation unit 312.

As shown, an initial monomer-containing feedstock 313 is combined with arecycle stream 320 comprising the hydrocarbon to form combinedmonomer-containing feedstock 304. Combined monomer-containing feedstock304, hydrogen feedstock 306 and catalyst feed 305 are directed toreaction vessel 301. The combined monomer-containing feedstock 304comprises an α-olefin (e.g., a C₈-C₁₂ α-olefin such as 1-decene), ahydrocarbon (e.g., a C₈-C₁₂ saturated hydrocarbon such as one or moredecanes or a hydrocarbon having a 50° C. vapor pressure within 20%,e.g., within 10% or within 5%, of the α-olefin) derived from the crudePAO product, optionally one or more minor monomers and optionally asolvent. As indicated above, the hydrocarbon preferably has the samenumber of carbon atoms as the α-olefin. The catalyst feed 305 comprisesa catalyst system, which preferably comprises a polymerization catalyst(preferably a metallocene procatalyst), a suitable co-catalyst(preferably an aluminoxane such as MAO), and optionally an anionicmetalloid-containing component (e.g., a borane or a borate), asdescribed above. The catalyst feed 305 may also include a catalystsolvent, such as toluene. Hydrogen feedstock 306 comprises hydrogen gas.In another embodiment, not shown, the hydrogen may be added to themonomer-containing feedstock 304, which is then directed to reactionvessel 301. Reaction vessel 301 also preferably includes a vent line,not shown, for venting gaseous components therefrom.

In reaction vessel 301 shown in FIG. 3, the monomers contact thepolymerization catalyst, the hydrocarbon, and hydrogen under conditionseffective to form the PAO, preferably a highly saturated PAO. Crude PAOproduct is yielded from the reaction vessel 301 via crude PAO stream 307and directed to a catalyst separation unit 302. As shown, the catalystseparation unit comprises a catalyst removal column, which preferably ispacked with one or more materials capable of deactivating the catalystand preferably separating the catalyst from the crude PAO product toform a reduced catalyst PAO stream 308, which is directed to separationzone 303.

In FIG. 3, separation zone 303 comprises first flash vessel 321, secondflash vessel 311 and one or more separation units 312 (one is shown) andpreferably is capable of efficiently separating the PAO product from theother components contained in reduced catalyst PAO stream 308.Separation zone 303 also preferably is capable of efficiently separatinga weight majority of the following components from reduced catalyst PAOstream 308 in separate streams: (1) the hydrocarbon, e.g., a decane; and(2) lighter components (for example, catalyst solvent such as toluene).As used herein, the term “lighter components” means components having avapor pressure less than the vapor pressure of the major hydrocarboncontained in crude PAO stream 307.

As shown, separation zone 303 separates the reduced catalyst PAO stream308 into first stage overhead stream 322, second stage overhead stream314, third overhead stream 316, and purified PAO product stream 310.

In the embodiment shown, reduced catalyst PAO stream 308 is directed tofirst flash vessel 321, where a rough separation is made between thelighter components contained in reduced catalyst PAO stream 308 andcomponents having a vapor pressure greater than the lighter components,e.g., PAO product, unreacted monomer and the hydrocarbon. Specifically,flash vessel 321 forms first overhead stream 322 and first bottomsstream 323. First overhead stream 322 preferably comprises a weightmajority, e.g., at least 80 weight percent, at least 95 weight percent,at least 98 weight percent or at least 99 weight percent of the lightercomponents, e.g., catalyst solvent such as toluene, contained in thereduced catalyst PAO stream 308. First overhead stream 322 preferablycomprises less than 20 weight percent, e.g., less than 10 weight percentor less than 5 weight percent, of the hydrocarbon (e.g., the C₈-C₁₂saturated hydrocarbon such as one or more decanes or the hydrocarbonhaving a 50° C. vapor pressure within 20%, e.g., within 10% or within5%, of the α-olefin) contained in reduced catalyst PAO stream 308. Firstbottoms stream 323 preferably comprises a weight majority, e.g., atleast 80 weight percent, at least 95 weight percent, at least 98 weightpercent or at least 99 weight percent of the PAO contained in thereduced catalyst PAO stream 308. First bottoms stream 323 alsopreferably comprises a weight majority, e.g., at least 80 weightpercent, at least 95 weight percent, at least 98 weight percent or atleast 99 weight percent of the hydrocarbon contained in the reducedcatalyst PAO stream 308. First bottoms stream 323 also preferablycomprises a weight majority, e.g., at least 80 weight percent, at least95 weight percent, at least 98 weight percent or at least 99 weightpercent of the unreacted monomer contained in the reduced catalyst PAOstream 308.

A rough separation of first bottoms stream 323 is then performed toseparate the PAO product contained therein from the bulk of theunreacted monomer and C₈-C₁₂ saturated hydrocarbons contained therein.Specifically, second flash vessel 311 separates first bottoms stream 323into second overhead stream 314 and second bottoms stream 315. Secondoverhead stream 314 preferably comprises a weight majority, e.g., atleast 80 weight percent, at least 95 weight percent, at least 98 weightpercent or at least 99 weight percent of the hydrocarbon contained infirst bottoms stream 323. Second overhead stream 314 also preferablycomprises a weight majority, e.g., at least 80 weight percent, at least95 weight percent, at least 98 weight percent or at least 99 weightpercent of the unreacted monomer contained in first bottoms stream 323.Second bottoms stream 315 preferably comprises a weight majority, e.g.,at least 80 weight percent, at least 95 weight percent, at least 98weight percent or at least 99 weight percent of the PAO contained infirst bottoms stream 323. Optionally, second overhead stream 314 isseparated into a first aliquot portion 317 and a second aliquot portion318. Second aliquot portion 318 is removed from the reaction system 300as a purge stream in order to avoid the undesirable build up of lightcontaminants in the reaction system.

Second bottoms stream 315 is then directed to separation unit 312, wherea third separation is made between the PAO product and any lightcomponents (e.g., unreacted monomer, C₈-C₁₂ saturated hydrocarbon)contained in second bottoms stream 315. Specifically, separation unit312 forms third overhead stream 316 and purified PAO product stream 310.Third overhead stream 316 preferably comprises a weight majority, e.g.,at least 80 weight percent, at least 95 weight percent, at least 98weight percent or at least 99 weight percent of the hydrocarbon (e.g.,the C₈-C₁₂ saturated hydrocarbon such as one or more decanes or thehydrocarbon having a 50° C. vapor pressure within 20%, e.g., within 10%or within 5%, of the α-olefin) contained in the second bottoms stream315. As described above with reference to second overhead stream 314, analiquot portion, not shown, of third overhead stream 316 may be removedfrom the reaction system 300 as a purge stream. Purified PAO productstream 310 preferably comprises a weight majority, e.g., at least 80weight percent, at least 95 weight percent, at least 98 weight percentor at least 99 weight percent of the PAO contained in the second bottomsstream 315. Ideally, purified PAO product stream 310 comprisessubstantially pure PAO product.

In the embodiment of FIG. 3, as in FIG. 2, the first aliquot portion 317of first second overhead stream 314 is combined with third overheadstream 316 to form recycle stream 320, which is added to initialmonomer-containing stream 313 to form combined monomer-containingfeedstock 304. In this manner, the hydrocarbons and unreacted monomerfrom second overhead stream 314 and third overhead stream 316 arerecycled to reaction vessel 301, surprisingly and unexpectedly resultingin improved overall selectivity and yield. In addition, first flashvessel 321 advantageously removes lighter components (e.g., catalystsolvent) from the reaction system, thereby preventing their recycle backto reaction vessel 306 and effectively maximizing selectivity for theoverall process.

Various features and aspects of the present invention are illustratedfurther in the examples that follow. While these examples are presentedto show one skilled in the art how to operate within the scope of theinvention, they are not intended in any way to serve as a limitationupon the scope of the invention.

EXAMPLES Decane Used in Polymerization

Examples 1-3 demonstrate the unexpected increase for selectivity andyields when polymerizing 1-decene in the presence of n-decane. Theselectivity %, yield %, conversion % and Kv, cSt at 100° C. are as shownbelow in TABLE 1.

Example 1 (Comparative)

A two liter stainless-steel oil-heated autoclave reactor was equippedwith an agitator, 1-decene delivery system (pressurized flow and massflow control), catalyst and hydrogen delivery system (pressurized flowand mass flow control with sub-surface hydrogen sparge) capable ofachieving 300 psig (2068 kPa) pressure and 150° C. and overflowing at 1liter liquid volume. The system was equipped with a closed looptemperature, pressure and flow control (on hydrogen, decene, andcatalyst). Product was collected in a product tank for subsequentcatalyst deactivation and analysis.

The catalyst solution was pre-made as follows. In a glove box free ofoxygen, 136.16 g dry toluene and 29.08 g of 10% methylamuminoxane (MAO)in toluene was added to a clean 1 liter bottle equipped with dip-tubecap. The MAO was mixed for 30 minutes. 0.080 g diphenylmethylene(cyclopentadienyl-9-fluorenyl)zirconium dichloride (CpFlu) catalyst wasadded to the 1 liter bottle and the resulting mixture was mixed anadditional 15 minutes. The bottle was sealed with the dip tube cap.

A reactor containing 1 liter residual crude polydecene was heated to115° C. and pressurized with hydrogen to 240 psig (1655 kPag). Thecatalyst solution bottle was connected to a high pressure liquidchromatography (HPLC) piston pump which was used to feed the catalyst tothe reactor. A 10 liter decene feed tank was filled with dry 1-decene,treated by pumping through a packed column containing 3 Å molecularsieves and alumina. The reaction began (time=0) by simultaneouslystarting the catalyst feed pump feeding at 1 ml/min catalyst solution,the 1-decene flow controller at 2 L/hr and the hydrogen flow controllerat 500 standard cubic centimeters/minute (sccm). After 2.5 hours, thereactor reached steady state and a sample was taken. Unreacted deceneand decane in the sample was removed by vacuum evaporation (240° C., 5mm Hg absolute pressure) and purged. The viscosity of the sample wasdetermined by ASTM D445. Conversion, selectivity, and yield were alsodetermined and are shown in TABLE 1, below.

Example 2

Example 2 simulates a recycle operation of unreacted 1-decene and1-decane. A 2 liter stainless-steel oil-heated autoclave reactor wasequipped with an agitator, 1-decene delivery system (pressurized flowand mass flow control), catalyst and 1-decane delivery system (HPLCpumps) and hydrogen delivery system (pressurized flow and mass flowcontrol with sub-surface hydrogen sparge) capable of achieving 300 psig(2068 kPag) pressure and 150° C. and overflowing at 1 liter liquidvolume. The monomer used contained about 95 wt. % 1-decene, about 3 wt.% other decene, and about 2 wt. % other hydrocarbons. The decane usedcontained about 98 wt. % 1-decane, about 1.5 wt. % other decane andabout 0.5 wt. % unknown hydrocarbons. The system was equipped withclosed loop temperature, pressure and flow control (on hydrogen,decene/decane, and catalyst). Product was collected in a product tankfor subsequent catalyst deactivation and analysis.

The catalyst solution was pre-made according to the procedure of Example1.

Two clean 1 liter bottles equipped with a dip-tube were separatelyfilled with 1 liter each of substantially pure decane. Decene has ahigher vapor pressure than decane by about 20% at 50° C. and 10% at 150°C.

A reactor containing residual polydecene was heated to 115° C. andpressurized with hydrogen to 240 psig (1655 kPag). The catalyst solutionbottle and decane solution bottles were connected to separate highpressure liquid chromatography (HPLC) piston pumps which were used tofeed catalyst and decane to the reactor. A 10 liter decene feed tank wasfilled with dry 1-decene, treated by pumping through a packed columncontaining 3 Å molecular sieves and alumina. The reaction began (time=0)by simultaneously starting the catalyst feed pump feeding at 1 ml/min ofcatalyst solution, the decane feed pump at 0.5 L/hr decane, the deceneflow controller at 1.5 L/hr thus achieving 25% decane in the reactor andthe hydrogen flow controller at 500 standard cubic centimeters/minute(sccm).

Average residence time was calculated by dividing the liquid volume inthe reactor by the liquid flow rates. In this example, 1 liter liquidvolume divided by (1.5+0.5) or 2 liters/hr=30 minutes residence time.After feeding decane/decene/hydrogen and the catalyst solution forapproximately 4 reactor turnovers (residence times) which was 2 hourstotal, the reactor reached 1-e⁻⁴ or 98.2% of its steady-statecomposition. The reaction was then shut down and the product sampled foranalysis.

TABLE 1, below, compares viscosity, conversion, selectivity and yielddata from Examples 1 and 2.

TABLE 1 Example Kv, cSt at 100° C. Conversion % Selectivity % Yield % 1110 89.1% 85.2% 75.9% 2 105 87.2% 91.3% 79.6%

As shown, the overall yield was much lower in Example 1 owing to thelower selectivity (due to not adding decane) and the fact that unreacteddecene was purged. The addition of decane in Example 2 improved singlepass and overall selectivity (simulating decane recycle). Adding decenein Example 2 (simulated decene recycle) also improved overall conversionsince the unreacted decene was not purged. Note that selectivity may beincreased by also increasing the Kv. However, as shown in Example 2, theselectivity surprisingly and unexpectedly increased even though the Kvincreased only slightly relative to comparative Example 1.

Example 3

A material balance analysis, based on conversion, selectivity and yielddata from Example 2, was performed for the reaction system describedabove with reference to FIG. 2, in which the monomer comprised 1-decene,with decane/decene recycle and CpFlu catalyst. The conditions for thematerial balance are provided below in TABLE 2. FIG. 4 provides therelative amounts of components contained in the various streams shown inFIG. 2. TABLE 3 provides the Conversion, selectivity and yield for thematerial balance analysis were derived from Example 2 and are providedbelow in TABLE 3.

TABLE 2 CONDITIONS FOR MATERIALS BALANCE ANALYSIS OF EXAMPLE 1 Basis:1.05 MM lbs/yr (0.48 MM kg/yr) Laboratory Conditions Production: 7,446hrs/yr Cat Conc. 0.00075 moles/L Residence Time 30.00 min Cat. Flow 1.00Ml/min Reactor Vol. 25 gallons (95 L) MAO Ratio 750 mol/mol Zr PurgeFraction 0.177 MAO Frac. 0.1 Flash 0.980 Decene + 2.00 L/hr Overhead(w/w) Decane Evaporator 0.999 Decane fraction 0.25 Overhead (w/w)

TABLE 3 CONVERSION, SELECTIVITY & YIELD One Pass¹ Overall² Conversion0.872 1.000 Selectivity 0.913 0.891 Yield 0.796 0.891 ¹From combinedmonomer-containing stream 204 to crude PAO product stream 207. ²Fromdecene feed stream 213 to purified PAO product stream 210.

Residence Time Example 4

Using a similar system and catalyst as in Example 1, 1-decene waspolymerized without the presence of decane. At time (0), the reactionwas begun by simultaneously starting the catalyst feed pump at 2 ml/minof catalyst solution, the decene flow controller at 4.0 L/hr and thehydrogen flow controller at 1000 sccm. Average residence time wascalculated by dividing the liquid volume in the reactor by the liquidflow rates. In this example, 1 liter liquid volume divided by 4liters/hr=15 minutes residence time. After feeding decene/hydrogen andcatalyst solution for approximately 4 reactor turnovers (residencetimes) which was 1 hour total, the reactor reached 1-e⁻⁴ or 98.2% of itssteady-state composition. The Kv at 100° C. was measured at 147 cSt.Catalyst flow was kept proportional to decene flow in order to keepcatalyst concentration constant.

Example 5

The residence time was increased to 30 minutes by feeding 1.0 ml/min ofcatalyst solution, 2.0 l/hr of decene and 1000 sccm of hydrogen using asimilar process as in Example 4. The Kv at 100° C. was measured at 113cSt.

Example 6

The residence time was increased to 45 minutes by feeding 0.67 ml/min ofa catalyst solution, 1.3 l/hr of decene and 1000 sccm of hydrogen usinga similar process as in Example 4. The Kv at 100° C. was measured at 81cSt.

The conditions employed in Examples 4-6 and the resulting viscosities ofthe product PAOs are provided below in TABLE 4. FIG. 8 provides a chartplotting PAO viscosity as a function of residence time based on the datafrom Examples 4-6. As shown, Examples 4-6 surprisingly and unexpectedlydemonstrate that as residence time increased, the viscosity decreased.The viscosity was generally proportional to molecular weight. Thus, asshown in Example 5, a residence time of 30 minutes produced a PAO with ahighly desirable viscosity of about 100 cSt.

TABLE 4 Example 4 Example 5 Example 6 Reactor Liq. 1.0 1.0 1.0 Vol. (L)T (° C.) 115 115 115 Pressure 140; 1655 140; 1655 140; 1655 (psig; kPag)H₂ flow (sccm) 1000 1000 1000 Decene Flow 4.0 2.0 1.33 Rate (ml/min)Catalyst Flow 2.0 1.0 0.67 Rate (ml/min) Residence Time 15 30 45 (min)Viscosity (cSt) 147 113 81

Example 7 Structural Analysis of PAO

Polydecene was prepared in a similar fashion to Example 2, but the1-decene and decane were premixed to make a 30/70 wt % decane/1-decenemixture that was fed through the decene delivery system. The process wasrun at 130° C. and at 90 psig (621 kPag) and a catalyst mixture of 51.0grams dry toluene, 19.14 grams 10 wt. % MAO and 0.068 grams CpFlu wasadded at a rate of 0.5 ml/minute. The resulting product was analyzed in¹³C NMR. The upper portion of FIG. 5A provides a ¹³C NMR spectrum forExample 7 and the upper portion of FIG. 5B provides a more detailed ¹³CNMR spectrum in the region from 35.5 to 33.6 ppm. No discernible peaksare shown for FIG. 5A for Example 7 in the regions of 21 to 20 ppm or42.5 ppm, indicating a low degree of misinsertion or rearrangement.

Example 8 Property Analysis

Polydecene was prepared in a similar fashion to Example 2, but using140° C., 40 psig (276 kPag) and catalyst feed pump feeding at 1.5 ml/minof catalyst solution. Decane was fed at 1.0 L/hr decane, and the deceneflow controller was set at 2.0 L/hr. FIG. 6 provides a ¹³C NMR spectrumfor Example 8 and, when compared with FIG. 5, demonstrates thestructural similarity of Examples 7 and 8. A property analysis isprovided in TABLE 6, below.

Comparative Example A

Polydecene was prepared using a chromium catalyst through thepolymerization process described in U.S. Pat. No. 4,921,272, theentirety of which is incorporated herein by reference. A ¹³C NMRspectrum for the polydecene is provided in the lower portion of FIG. 5A.The lower portion of FIG. 5B provides a detailed ¹³C NMR spectrum in theregion from 35.5 to 33.6 ppm for Comparative Example A. The propertiesof the PAO formed in comparative Example A are shown below in TABLE 6.

FIG. 5A shows that the PAO sample from Example 7 has a much cleanerspectrum having fewer peaks than the PAO of comparative Example A,reflecting a less diverse structure than the polydecene from comparativeExample A.

The polydecene from comparative Example A has additional peaks in theregion of 28.0 and 36-37 ppm while there are no similar peaks in the PAOanalyzed in Example 7 (see FIG. 5A). As shown, when comparing the ¹³CNMR spectra of FIG. 5, the relative content (area) of comparativeExample A is greater than the PAO analyzed in Example 7 in the region of35.50 to 34.96 ppm, indicating the presence of greater isotacticity inthe PAO of comparative Example A. TABLE 5 compares the relative content(area) in the region of from 35.40 to 33.71 ppm from the spectra of FIG.5B.

TABLE 5 Relative Content (%) Shift Integral Range Comparative TriadPentad (PPM) (PPM) Example 7 Example A mm mmmm 35.40 35.50-35.35 0 4.5mmmr 35.24 35.35-35.09 0.9 10.5 rmmr 35.04 35.09-34.96 2.9 6.4 mr mmrr34.86 34.96-34.75 12.2 10.7 mmrm/rmrr 34.68 34.75-34.56 13.8 9.6 rmrm34.52 34.56-34.40 14.4 9.3 rr rrrr 34.30 34.40-34.29 13.8 8.4 rrrm 34.1934.29-34.08 22.2 17.7 mrrm 34.03 34.08-33.71 19.6 22.9

Comparative Example B

Polydecene was prepared through the polymerization process described inU.S. Pat. No. 4,532,061, the entirety of which is incorporated herein byreference. FIG. 7 illustrates a ¹³C NMR spectrum for the PAO ofComparative Example B. The spectrum in FIG. 7 is not nearly as clean asthe spectra shown for Example 7 in FIG. 5A, indicating a much morediverse structure than the structure formed in Example 7. FIG. 7 showsthat the polydecene of Comparative Example B has a greater degree oftail-to-tail insertions than the PAOs of Example 7 or ComparativeExample A based on the presence of a peak in the region of 21-20 ppm.Further, FIG. 7 shows a greater degree of head-to-head insertions by thepresence of a peak in the region of 42.5 ppm. Minor head-to-tailconfiguration is evidenced by FIG. 7 because there is only a marginallydiscernible peak in the region of 41-40 ppm.

The properties of the polydecene of Examples 7 and 8 are provided belowin TABLE 6 and are comparable to the polydecene of comparative ExamplesA and B, even though the polydecene of these examples had differentstructures from those of comparative Examples A and B, as shown in FIGS.5A, 5B, 6 and 7.

TABLE 6 PROPERTY COMPARISON Comparative Comparative Example 7 Example 8Example A Example B Kv, cSt at 100° C. 280.0 102 158.4 99.73 GPC, Mw **6,241 9,129 5,448 GPC, Mn ** 3,192 3,818 3,372 Pd ** 2.0 2.39 1.65 %Propylene ** 18.6 18.8 20.7

Example 9 Catalyst Removal by Column Treatment

Polydecene prepared in a similar fashion to Example 7, but using 180psig (1241 kPag) and a catalyst mixture of 106.3 grams dry toluene,41.08 grams 10% MAO and 0.14 grams CpFlu added at a rate of 0.5ml/minute, was deactivated using a column packed with acid clay, FiltrolF-24 manufactured by Engelhard Corporation. A metals analysis, used todetermine the removal of catalyst, shown in TABLE 7, below, demonstratedthe effectiveness in comparing the column deactivated polymer to thepredeactivated polymer.

TABLE 7 Example 9 Example 9 Metals, ppm, ASTM D-5185 PredeactivationColumn Deactivated Aluminum 195 <1 Boron <1 <1 Calcium <1 <1 Magnesium<1 <1 Potassium <1 <1 Sodium <1 <1 Silicon <1 <1

Any feature described or claimed with respect to any disclosedimplementation may be combined in any combination with any one or moreother feature(s) described or claimed with respect to any otherdisclosed implementation or implementations, to the extent that thefeatures are not necessarily technically incompatible, and all suchcombinations are within the scope of the present invention. Furthermore,the claims appended below set forth some non-limiting combinations offeatures within the scope of the invention, but also contemplated asbeing within the scope of the invention are all possible combinations ofthe subject matter of any two or more of the claims, in any possiblecombination, provided that the combination is not necessarilytechnically incompatible.

1. A process for forming a polyalphaolefin, comprising the steps of: (a)adding a C₈-C₁₂ α-olefin, a C₈-C₁₂ saturated hydrocarbon, hydrogen, anda catalytically effective amount of a catalyst system to a reactionvessel, wherein the C₈-C₁₂ saturated hydrocarbon is fed to the reactionvessel in an amount ranging from 5 to 70 weight percent, based on thecombined weight of the C₈-C₁₂ α-olefin and the C₈-C₁₂ saturatedhydrocarbon fed to the reaction vessel; and (b) polymerizing the C₈-C₁₂α-olefin in the reaction vessel in the presence of the C₈-C₁₂ saturatedhydrocarbon, the hydrogen, and the catalyst system under conditionseffective to form the polyalphaolefin.
 2. The process of claim 1,wherein the C₈-C₁₂ saturated hydrocarbon is fed to the reaction vesselin an amount ranging from 10 to 50 weight percent, based on the combinedweight of the C₈-C₁₂ α-olefin and the C₈-C₁₂ saturated hydrocarbon fedto the reaction vessel.
 3. The process of claim 1, wherein the C₈-C₁₂saturated hydrocarbon is fed to the reaction vessel in an amount rangingfrom 15 to 30 weight percent, based on the combined weight of the C₈-C₁₂α-olefin and the C₈-C₁₂ saturated hydrocarbon fed to the reactionvessel.
 4. The process of claim 1, wherein the C₈-C₁₂ α-olefin and theC₈-C₁₂ saturated hydrocarbon have the same number of carbon atoms. 5.The process of claim 1, wherein the C₈-C₁₂ α-olefin comprises 1-deceneand the C₈-C₁₂ saturated hydrocarbon comprises n-decane.
 6. The processof claim 1, wherein the process initially forms a crude polyalphaolefinproduct comprising the polyalphaolefin, unreacted monomer, and C₈-C₁₂saturated hydrocarbon, the process further comprising the steps of: (c)separating the C₈-C₁₂ saturated hydrocarbons from the crudepolyalphaolefin product; and (d) adding at least a portion of theseparated C₈-C₁₂ saturated hydrocarbons to the reaction vessel.
 7. Theprocess of claim 6, wherein a first portion of the separated C₈-C₁₂saturated hydrocarbons is purged, and a second portion of the separatedC₈-C₁₂ saturated hydrocarbons is added to the reaction vessel.
 8. Theprocess of claim 6, wherein the unreacted monomer is separated from thecrude polyalphaolefin product with the separated C₈-C₁₂ saturatedhydrocarbons and is added to the reaction vessel with the separatedC₈-C₁₂ saturated hydrocarbons.
 9. The process of claim 6, wherein theprocess has an overall conversion greater than 95 percent.
 10. Theprocess of claim 6, wherein the process has an overall yield greaterthan 85 percent.
 11. The process of claim 6, wherein the process iscontinuous.
 12. The process of claim 11, wherein the C₈-C₁₂ saturatedhydrocarbons are maintained in the reaction vessel at a level of from 8to 40 weight percent, based on the combined weight of the C₈-C₁₂α-olefin, the C₈-C₁₂ saturated hydrocarbon and the polyalphaolefincontained in the reaction vessel.
 13. The process of claim 11, wherein acatalyst in the catalyst system is added to the reaction vessel in acatalyst solution comprising a catalyst solvent and the catalyst. 14.The process of claim 13, wherein the catalyst solvent is separated fromthe crude polyalphaolefin product with the C₈-C₁₂ saturated hydrocarbonsand is added to the reaction vessel with the separated C₈-C₁₂ saturatedhydrocarbons.
 15. The process of claim 13, wherein the catalyst solventis separated from the crude polyalphaolefin product separately from theC₈-C₁₂ saturated hydrocarbons.
 16. The process of claim 6, wherein theprocess further comprises the step of: (e) contacting the crudepolyalphaolefin product with solid adsorbent particles packed in acatalyst removal column under conditions effective to selectively adsorbspent catalyst from the polyalphaolefin reaction system.
 17. The processof claim 1, wherein the catalyst system comprises diphenylmethylene(cyclopentadienyl-9-fluorenyl)zirconium dichloride.
 18. The process ofclaim 17, wherein the catalyst system further comprises an aluminoxanecocatalyst.
 19. The process of claim 1, wherein the polyalphaolefin hasan Iodine Number of from 0.2 to
 5. 20. The process of claim 1, whereinthe C₈-C₁₂ α-olefin is added to the reaction vessel in an amount from 70to 93 weight percent, and the C₈-C₁₂ saturated hydrocarbon is added tothe reaction vessel in an amount from 7 to 30 weight percent, based onthe combined weight of the C₈-C₁₂ α-olefin and the C₈-C₁₂ saturatedhydrocarbon fed to the reaction vessel.
 21. The process of claim 1,wherein the polyalphaolefin has a kinematic viscosity at 100° C. from 50to 500 centistokes.
 22. The process of claim 1, wherein thepolyalphaolefin has a kinematic viscosity at 100° C. from 50 to 150centistokes.
 23. The process of claim 1, wherein the process has a PAOselectivity of from 90% to 100%.
 24. The process of claim 1, wherein theC₈-C₁₂ α-olefin is polymerized at a temperature from 105° C. to 170° C.25. The process of claim 1, wherein the reaction vessel is pressurizedat a pressure from 520 to 720 kPag.
 26. The process of claim 1, whereinthe polyalphaolefin has a residence time in the reaction vessel of from10 to 60 minutes.
 27. A process for forming a polyalphaolefin,comprising the steps of: (a) adding an α-olefin, a hydrocarbon having a50° C. vapor pressure within 20% of the vapor pressure of the α-olefin,hydrogen, and a catalytically effective amount of a catalyst system to areaction vessel; and (b) polymerizing the α-olefin in the reactionvessel in the presence of the hydrocarbon, the hydrogen, and thecatalyst system under conditions effective to form the polyalphaolefin.28. The process of claim 27, wherein the hydrocarbon has a 50° C. vaporpressure within 10% of the vapor pressure of the α-olefin.
 29. Theprocess of claim 27, wherein the hydrocarbon has a 50° C. vapor pressurewithin 5% of the vapor pressure of the α-olefin.
 30. The process ofclaim 27, wherein the hydrocarbon is added to the reaction vessel in anamount ranging from 10 to 50 weight percent, based on the combinedweight of the α-olefin and the hydrocarbon fed to the reaction vessel.31. The process of claim 27, wherein the hydrocarbon comprises asaturated hydrocarbon having an equal number of carbon atoms, within 1carbon atom, as the α-olefin.
 32. The process of claim 27, wherein theα-olefin and the hydrocarbon have the same number of carbon atoms. 33.The process of claim 27, wherein the α-olefin comprises 1-decene and thehydrocarbon comprises n-decane.
 34. The process of claim 27, wherein theprocess initially forms a crude polyalphaolefin product comprising thepolyalphaolefin, unreacted monomer, and C₈-C₁₂ saturated hydrocarbons,the process further comprising the steps of: (c) separating a weightmajority of the hydrocarbon from the crude polyalphaolefin product; and(d) adding at least a portion of the separated hydrocarbon to thereaction vessel.
 35. The process of claim 34, wherein a first portion ofthe separated saturated hydrocarbon is purged, and a second portion ofthe separated saturated hydrocarbon is added to the reaction vessel. 36.The process of claim 34, wherein the unreacted monomer is separated fromthe crude polyalphaolefin product with the separated hydrocarbons and isadded to the reaction vessel with the separated hydrocarbons.
 37. Theprocess of claim 34, wherein the process further comprises the step of:(e) contacting the crude polyalphaolefin product with solid adsorbentparticles packed in a catalyst removal column under conditions effectiveto selectively adsorb spent catalyst from the polyalphaolefin reactionsystem.
 38. The process of claim 27, wherein the process has an overallconversion greater than 95 percent.
 39. The process of claim 27, whereinthe process has an overall yield greater than 85 percent.
 40. Theprocess of claim 27, wherein the process is a continuous.
 41. Theprocess of claim 40, wherein the hydrocarbon is maintained in thereaction vessel at a level of from 8 to 40 weight percent, based on thecombined weight of the α-olefin, the hydrocarbon and the polyalphaolefinin the reaction vessel.
 42. The process of claim 40, wherein a catalystin the catalyst system is added to the reaction vessel in a catalystsolution comprising a catalyst solvent and the catalyst.
 43. The processof claim 42, wherein the catalyst solvent is separated from the crudepolyalphaolefin product with the hydrocarbon and is added to thereaction vessel with the separated hydrocarbon.
 44. The process of claim42, wherein the catalyst solvent is separated from the crudepolyalphaolefin product separately from the hydrocarbon.
 45. The processof claim 27, wherein the catalyst system comprises diphenylmethylene(cyclopentadienyl-9-fluorenyl)zirconium dichloride.
 46. The process ofclaim 45, wherein the catalyst system further comprises an aluminoxanecocatalyst.
 47. The process of claim 27, wherein the polyalphaolefin hasan Iodine Number of from 0.2 to
 5. 48. The process of claim 27, whereinthe α-olefin is added to the reaction vessel in an amount from 70 to 93weight percent, and the hydrocarbon is added to the reaction vessel inan amount from 7 to 30 weight percent, based on the combined weight ofthe α-olefin and the hydrocarbon fed to the reaction vessel.
 49. Theprocess of claim 27, wherein the polyalphaolefin has a kinematicviscosity at 100° C. from 50 to 500 centistokes.
 50. The process ofclaim 27, wherein the polyalphaolefin has a kinematic viscosity at 100°C. from 50 to 150 centistokes.
 51. The process of claim 27, wherein theprocess has a PAO selectivity of from 90% to 100%.
 52. The process ofclaim 27, wherein the α-olefin is polymerized at a temperature from 105°C. to 170° C.
 53. The process of claim 27, wherein the reaction vesselis pressurized at a pressure from 520 to 720 kPag.
 54. The process ofclaim 27, wherein the polyalphaolefin has a residence time in thereaction vessel of from 15 to 45 minutes.
 55. A reaction system forforming polyalphaolefin, comprising: (a) a reaction vessel in which aC₈-C₁₂ α-olefin contacts a C₈-C₁₂ saturated hydrocarbon, hydrogen, and acatalytically effective amount of catalyst system under conditionseffective to form a crude polyalphaolefin stream; (b) a catalystseparation unit in fluid communication with the reaction vessel forseparating spent catalyst from the crude polyalphaolefin stream andforming a reduced catalyst polyalphaolefin stream; and (c) a separationzone in fluid communication with the catalyst separation unit forseparating the reduced catalyst polyalphaolefin stream into a purifiedpolyalphaolefin stream and a recycle stream comprising the C₈-C₁₂saturated straight-chain hydrocarbon and unreacted C₈-C₁₂ α-olefin,wherein the recycle stream is in fluid communication between theseparation zone and the reaction vessel.
 56. The reaction system ofclaim 55, wherein the reduced catalyst polyalphaolefin stream furthercomprises catalyst solvent, and wherein the separation zone comprises aflash vessel for removing the catalyst solvent from the reduced catalystpolyalphaolefin stream.
 57. The reaction system of claim 55, wherein thecatalyst separation unit comprises a catalyst separation columncomprising a solid adsorbent selected from the group consisting ofacidic clay, zeolites, calcium oxide, magnesium oxide, silicates andmixtures thereof.
 58. The reaction system of claim 55, wherein theC₈-C₁₂ α-olefin and the C₈-C₁₂ saturated hydrocarbon have the samenumber of carbon atoms.
 59. The reaction system of claim 55, wherein theC₈-C₁₂ α-olefin comprises 1-decene and the C₈-C₁₂ saturated hydrocarboncomprises n-decane.
 60. The reaction system of claim 55, wherein thereaction system provides an overall conversion greater than 95 percent.61. The reaction system of claim 55, wherein the reaction system has anoverall yield greater than 85 percent.
 62. The reaction system of claim55, wherein the reaction system is a continuous reaction system.
 63. Thereaction system of claim 55, wherein the reduced catalystpolyalphaolefin stream further comprises catalyst solvent, and whereinthe catalyst solvent is separated by the separation zone into therecycle stream.
 64. The reaction system of claim 55, wherein thecatalyst system comprises diphenylmethylene(cyclopentadienyl-9-fluorenyl)zirconium dichloride.
 65. The reactionsystem of claim 64, wherein the catalyst system further comprises analuminoxane cocatalyst.
 66. The reaction system of claim 55, wherein theC₈-C₁₂ α-olefin is polymerized at a temperature from 105° C. to 170° C.67. The reaction system of claim 55, wherein the reaction vessel ispressurized at a pressure from 520 to 720 kPag.
 68. A reaction systemfor forming polyalphaolefin, comprising: (a) a reaction vessel in whichan α-olefin contacts a hydrocarbon having a 50° C. vapor pressure within20% of the α-olefin, hydrogen, and a catalytically effective amount ofcatalyst system under conditions effective to form a crudepolyalphaolefin stream; (b) a catalyst separation unit in fluidcommunication with the reaction vessel for separating spent catalystfrom the crude polyalphaolefin stream and forming a reduced catalystpolyalphaolefin stream; and (c) a separation zone in fluid communicationwith the catalyst separation unit for separating the reduced catalystpolyalphaolefin stream into a purified polyalphaolefin stream and arecycle stream comprising the hydrocarbon and unreacted α-olefin,wherein the recycle stream is in fluid communication between theseparation zone and the reaction vessel.
 69. The reaction system ofclaim 68, wherein the hydrocarbon has a 50° C. vapor pressure within 10%of the vapor pressure of the α-olefin.
 70. The reaction system of claim68, wherein the hydrocarbon has a 50° C. vapor pressure within 5% of thevapor pressure of the α-olefin.
 71. The reaction system of claim 68,wherein the reduced catalyst polyalphaolefin stream further comprisescatalyst solvent, and wherein the separation zone comprises a flashvessel for removing the catalyst solvent from the reduced catalystpolyalphaolefin stream.
 72. The reaction system of claim 68, wherein thecatalyst separation unit comprises a catalyst separation columncomprising a solid adsorbent selected from the group consisting ofacidic clay, zeolites, calcium oxide, magnesium oxide, silicates andmixtures thereof.
 73. The reaction system of claim 68, wherein thehydrocarbon comprises a saturated hydrocarbon having an equal number ofcarbon atoms, within 1 carbon atom, as the α-olefin.
 74. The reactionsystem of claim 68, wherein the α-olefin and the saturated hydrocarbonhave the same number of carbon atoms.
 75. The reaction system of claim68, wherein the α-olefin comprises 1-decene and the hydrocarboncomprises n-decane.
 76. The reaction system of claim 68, wherein thereaction system provides an overall conversion greater than 95 percent.77. The reaction system of claim 68, wherein the reaction system has anoverall yield greater than 85 percent.
 78. The reaction system of claim68, wherein the reaction system is a continuous reaction system.
 79. Thereaction system of claim 68, wherein the reduced catalystpolyalphaolefin stream further comprises catalyst solvent, and whereinthe catalyst solvent is separated by the separation zone into therecycle stream.
 80. The reaction system of claim 68, wherein thecatalyst system comprises diphenylmethylene(cyclopentadienyl-9-fluorenyl)zirconium dichloride.
 81. The reactionsystem of claim 80, wherein the catalyst system further comprises analuminoxane cocatalyst.
 82. The reaction system of claim 68, wherein theα-olefin is polymerized at a temperature from 105° C. to 170° C.
 83. Thereaction system of claim 68, wherein the reaction vessel is pressurizedat a pressure from 520 to 720 kPag.
 84. A catalyst removal column influid communication with a polyalphaolefin reaction vessel, wherein thecatalyst removal column is packed with solid adsorbent particlesconfigured to selectively adsorb spent catalyst from the polyalphaolefinreaction system.
 85. The catalyst removal column of claim 84, whereinsolid adsorbent particles are selected from the group consisting ofacidic clay, zeolites, calcium oxide, magnesium oxide, silicates andmixtures thereof.
 86. The catalyst removal column of claim 84, whereinsolid adsorbent particles comprise a metal oxide.
 87. The catalystremoval column of claim 84, wherein solid adsorbent particles have anaverage particle size of from 100 μm to 1 cm.
 88. The catalyst removalcolumn of claim 84, wherein the spent catalyst comprisesdiphenylmethylene (cyclopentadienyl-9-fluorenyl)zirconium dichloride.89. The catalyst removal column of claim 84, wherein the spent catalystfurther comprises an aluminoxane cocatalyst.
 90. A polyalphaolefincomprising from 0.5 to 5 mole % of mm triads and from 40 to 58 mole % ofrr triads.
 91. The polyalphaolefin of claim 90, wherein thepolyalphaolefin is formed by polymerizing one olefin monomer in thepresence of a bridged metallocene catalyst and hydrogen.
 92. Thepolyalphaolefin of claim 91, wherein the olefin monomer is a C₈-C₁₂olefin.
 93. The polyalphaolefin of claim 91, wherein the olefin monomeris 1-decene.
 94. The polyalphaolefin of claim 91, wherein the bridgedmetallocene catalyst is diphenylmethylene (cyclopentadienyl-9-fluorenyl)zirconium dichloride.
 95. The polyalphaolefin of claim 91, wherein themonomer is polymerizing the presence of an alkylaluminoxane co-catalyst.96. The polyalphaolefin of claim 91, wherein from 0.01 to 1.2 moles ofthe hydrogen are present per mole of the monomer.
 97. Thepolyalphaolefin of claim 90, wherein the polyalphaolefin comprises from37 to 59.5 mole % of mr triads.
 98. The polyalphaolefin of claim 90,wherein the polyalphaolefin is substantially free of a peak in a regionof from 27.0 to 29.0 ppm in a ¹³C NMR spectrum.
 99. The polyalphaolefinof claim 90, wherein the polyalphaolefin is substantially free of peaksin a region of about 20.0 ppm in a ¹³C NMR spectrum.
 100. Thepolyalphaolefin of claim 90, wherein the polyalphaolefin issubstantially free of peaks in a region of about 42.5 ppm in a ¹³C NMRspectrum.
 101. A process for forming a polyalphaolefin, comprising thestep of polymerizing in a reaction vessel a C₈-C₁₂ α-olefin in thepresence of hydrogen, and a catalytically effective amount of a catalystsystem under conditions effective to form the polyalphaolefin, whereinthe polyalphaolefin has an average residence time in the reaction vesselof greater than 1 minute, and wherein the polyalphaolefin has akinematic viscosity of less than 1000 cSt.
 102. The process of claim101, wherein the polyalphaolefin has an average residence time in thereaction vessel of greater than 5 minutes, and wherein thepolyalphaolefin has a kinematic viscosity of less than 200 cSt.
 103. Theprocess of claim 101, wherein the polyalphaolefin has an averageresidence time in the reaction vessel of greater than 10 minutes, andwherein the polyalphaolefin has a kinematic viscosity of less than 150cSt.